Heterocyclic compounds

ABSTRACT

Novel insecticides of the formula ##STR1## in which n is 1, 
     X is ##STR2## Y is N or ##STR3## Z is a 5- or 6-membered nitrogen-containing heterocyclic ring, and R to R 9  variously represent hydrogen or specified organic radicals.

This is a division, of application Ser. No. 557,292, filed Jul. 24,1990, now U.S. Pat. No. 5,204,360, which is a division of appl. Ser. No.347,836, filed May 4, 1989, now U.S. Pat. No. 5,001,138, which is adivision of appl. Ser. No. 068,991, filed Jul. 1, 1987, now U.S. Pat.No. 4,845,106, which is a division of appl. Ser. No. 821,621 filed Jan.21, 1986, now U.S. Pat. No. 4,742,060.

The present invention relates to novel heterocyclic compounds, toprocesses for their preparation, to their use as insecticides.

It has already been disclosed that not only certain nitromethylenederivatives have insecticidal function, for instance,1-benzyl-2-nitromethylene tetrahydropyrimidine (see DE-OS 2,514,402),but certain triazolidine derivatives have anti-tumor function againstgastrointestinal tumor (see Japanese Laid-Open Patent Publication196,877/1984).

Furthermore, 1-benzyl-2-nitroiminoimidazolidine has been described inCan. J. Chem., vol. 39, pages 1787-1796.

There have now been found novel heterocyclic compounds of the formula(I): ##STR4## wherein n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or an alkylgroup, R³ and R⁴ independently represent a hydrogen atom, a hydroxygroup or an alkyl group, where n represents 1, then R² may form a singlebond, together with R⁵,

X represents a sulfur atom, an oxygen atom, ##STR5## wherein R⁷represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxygroup, a benzyloxy group, an alkyl group which may be substituted by atleast one substituent selected from the class consisting of alkoxygroups, alkylthio groups, a cyano group, halogen atoms, dialkylaminogroups and trialkylsilyl, an alkenyl group which may be substituted by ahalogen atom, an alkynyl group which may be substituted by a halogenatom, a phenyl group which may be substituted by an alkyl group and/or ahalogen atom, a benzyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, amethoy group, halogen atoms, halomethyl groups, halomethoxy groups and anitro group, a formyl group, an alkenylcarbonyl group, an alkylcarbonylgroup which may be substituted by at least one substituent selected fromthe class consisting of alkoxy groups, a phenoxy group, alkylthiogroups, and halogen atoms, a benzoyl group which may be substituted byat least one substituent selected from the class consisting of halogenatoms, alkyl groups, halomethyl groups, alkoxy groups, haloalkoxy groupsand a nitro group, a benzylcarbonyl group which may be substituted by analkyl group and/or a halogen atom, an alkoycarbonyl group which may besubstituted by a halogen atom, an alkylthiocarbonyl group, asphenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of methyl group, a methoygroup, halomethyl group, halomethoxy groups, halogen atoms and a nitrogroup, a phenylthiocarbonyl group which may be substituted by a halogenatom and/or an alkyl group, a benzyloycarbonyl group, a monoalkyl- ordialkyl-aminocarbonyl group, a phenylaminocarbonyl group which may besubstituted by at least one substituent selected from the classconsisting of alkyl groups, haloalkyl groups and halogen atoms, abenzoylaminocarbonyl group which may be substituted by an alkyl groupand/or a halogen atom, a phenylsulfonylaminocarbonyl group which may besubstituted by an alkyl group and/or a halogen atom, a phenylthio groupwhich may be substituted by an alkyl group and/or a halogen atom, analkylsulfonyl group which may be substituted by a halogen atom, aphenylsulfonyl group which may be substituted by at least onesubstituent selected from the class consisting of alkyl groups, halogenatoms and a nitro group, an alkylcarbonylmethyl group, a phenacyl groupwhich may be substituted by a halogen atom and/or a alkyl group, anorganophosphono group, an organothionophosphono group, --CH₂ --W or--CO--W, wherein W represents a 5 to 6 membered heterocyclic group,containing at least one hetero atom selected from the class consistingof an oxygen atom, a sulfur atom and a nitrogen atom, which may besubstituted by at least one substituent selected from the classconsisting of halogen atoms, alkyl groups and haloalkyl groups,

R⁸ represents a hydrogen atom, an alkyl group, an aryl group or a benzylgroup,

Y represents a nitrogen atom or ##STR6## wherein R⁹ represents ahydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, abenzyloxy group, an alkyl group which may be substituted by at least onesubstituent selected from the class consisting of halogen atoms, ahydroxy group, alkoxy groups, alkylthio groups, a cyano group, mono- ordialkylamino groups, alkylcarbonyl groups, alkoxycarbonyl groups andphenoxycarbonyl groups, an alkenyl group which may be substituted by ahalogen atom, an alkynyl group, a phenyl group which may be substitutedby an alkyl group and/or a halogen atom, an alkylcarbonyl group whichmay be substituted by a halogen atom, an alkenylcarbonyl group, abenzoyl group which may be substituted by at least one substituentselected from the class consisting of halogen atoms, alkyl groups andalkoxy groups, an alkoxycarbonyl group which may be substituted by ahalogen atom, an alkylthiocarbonyl group, a phenoxycarbonyl group whichmay be substituted by at least one substituent selected from the classconsisting of halogen atoms, alkyl groups, alkoxy groups and a nitrogroup, a phenylthiocarbonyl group which may be substituted by an alkylgroup and/or a halogen atom, a phenylthiocarbonyl group which may besubstituted by an alkyl group and/or a halogen atom, a benzyloxycarbonylgroup, a benzoylaminocarbonyl group which may be substituted by an alkylgroup and/or a halogen atom, a phenylsulfonylaminocarbonyl group whichmay be substituted by an alkyl group and/or a halogen atom, analkylsulfonylaminocarbonyl group, an alkylthio group, an alkylsulfonylgroup which may be substituted by a halogen atom, a phenylthio groupwhich may be substituted by an alkyl group and/or a halogen atom, aphenylsulfonyl group which may be substituted by an alkyl group and/or ahalogen atom, in addition, R⁹ may from a bis-form of the formula (I),via a methylene group,

R represents a hydrogen atom or an alkyl group, and

Z represents a 5 to 6 membered heterocyclic group consisting at leastone hetero atom selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by at leastone substituent selected from the class consisting of halogen atoms,alkyl groups, haloalkyl groups, a nitro group, a cyano group, alkoxygroups, alkylthio groups, alkylsulfinyl groups, alkylsulfonyl groups,alkenyl groups, haloalkoxy group, haloalkylthio groups, haloalkenylgroups, acylamino groups, haloacylamino groups, alkoxycarbonyl groups, athiocyanato group, alkynyl groups, an amino group, alkylamino groups,dialkylamino groups, a carboxy group, a hydroxy group, a mercapto group,cycloalkyl groups, an oxo group, a thioxo group, haloalkenylthio groups,alkoyalkyl groups, alkoycarbonylamino groups, a carbamoyl group, acylgroups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, a formylgroup, aryl groups optionally substituted by a substituent selected fromthe class consisting of halogen atoms, alkyl groups, halogenoalkylgroups, alkoxy groups, a nitro group and a cyano group, aryloxy groupsoptionally substituted by the substituent as that shown for the abovearyl groups, and aralkyl groups optionally substituted by the samesubstituent as that shown for the aryl groups, provided that where R¹,R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneously,

X represents ##STR7## and Y represents and Z must not stand for thepyridyl group.

In the case of compounds according to the formula (I) having thefollowing formula (Ia): ##STR8## wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R,R⁹ and Z have the same meanings as stated above,

X¹ represents a sulfur atom, a oxygen atom or the following group##STR9## R¹⁰ means, in the definition of R⁷, other groups than acylgroups including sulfonyl groups and phosphono groups,

the compounds of the formula (Ia) are obtained when

(a) the compounds of the formula (II) ##STR10## wherein n, R¹, R², R³,R⁴, R⁵, R⁶, R, X¹ and Z have the same meanings as stated above,

are reacted with the compounds of the formula (III) ##STR11## wherein R'represents a lower alkyl or a benzyl group, or the two R's may from aring, together with two sulfur atoms to which they are bonded and R⁹ hasthe same meaning as stated above,

if appropriate, in the presence of inert solvents,

(b) the compounds of the above formula (II) are reacted with thecompounds of the formula (IV) ##STR12## wherein Hal represents a halogenatom and R" represents a hydrogen atom, a halogen atom or a lower alkylgroup,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors, or

(c) the compounds of the above formula (II) are reacted with thecompounds of the formula (V) ##STR13## wherein Hal and R" have the samemeanings as stated above, if appropriate, in the presence of inertsolvents and in the presence of acid acceptors.

In the case of compounds according to the formula (I) having thefollowing formula (Ib): ##STR14## wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R,X¹ and Z have the same meanings as stated above,

the compounds of the formula (Ib) are obtained when

(d) the compounds of the aforesaid formula (II) are reacted withnitroguanidine of the following formula ##STR15## if appropriate, in thepresence of inert solvents.

In the case of the formula (I) having the following formula (Ic)##STR16## wherein n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z have the samemeanings as stated above,

the compounds of the formula (Ic) are obtained when

(e) the compounds of the formula (VI) ##STR17## wherein n, R¹, R², R³,R⁴, R⁵, R⁶, X, R and Z have the same meanings as stated above,

are reacted with fuming nitric acid, if appropriate, in the presence ofinert solvent.

The compounds of the formula (I) are obtained when

(f) the compounds of the formula (VII) ##STR18## wherein n, R¹, R², R³,R⁴, R⁵, R⁶, X and Y have the same meanings as stated above,

are reacted with the compounds of the formula (VIII) ##STR19## wherein Rand Z have the same meaning as stated above,

M represents a halogen atom or --OSO₂ T, and

T represents a lower alkyl group, a phenyl group or a tolyl group,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors.

The novel heterocyclic compounds exhibit powerful insecticidalproperties.

Surprisingly, the heterocyclic compounds according to the inventionexhibit a substantially greater and much more excellent insecticidalaction than the closest known compounds from the aforementioned priorart.

In addition, the heterocyclic compounds according to the invention alsoexhibit a remarkable insecticidal action against harmful insects, inparticular sucking insects typified by insects of Hemiptera such asaphids, plant hoppers and leaf hoppers, which have acquired resistanceto organic phosphate and carbamate type-insecticides caused by long termuse.

Among the novel heterocyclic compounds according to the invention, ofthe formula (I), preferred compounds are those in which

n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or an alkylgroup having 1 to 5 carbon atoms, R³ and R⁴ independently represent ahydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbonatoms,

X represents a sulfur atom, an oxygen atom, ##STR20## R⁷ represents ahydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, ahydroxy group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxygroup, an alkyl group having 1 to 4 carbon atoms which may besubstituted by at least one member selected from the class consisting ofalkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromineatom, a dimethylamino group and trimethylsilyl, an alkenyl group having2 to 3 carbon atoms which may be substituted by a chlorine atom, analkynyl group having 2 to 3 carbon atoms, a benzyl group which may besubstituted by at least one substituent selected from the classconsisting of a methyl group, a methoxy group, a fluorine atom, achlorine atom, a bromine atom and a nitro group, a formyl group, analkenylcarbonyl group having an alkenyl part with 2 to 3 carbon atoms,an alkyl group having 1 to 5 carbon atoms which may be substituted by atleast one substituent selected from the class consisting of a methoxygroup, a phenoxy group, a fluorine atom, a chlorine atom and a bromineatom, a benzoyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom, a methyl group, a trifluoromethyl group,a methoxy group, a difluoromethoxy group, a trifluoromethoxy group and anitro group, a benzylcarbonyl group which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom and a bromine atom, an alkoxycarbonyl group having analkyl with 1 to 4 carbon atoms which may be substituted by a fluorineatom and/or a chlorine atom, an alkylthiocarbonyl group having an alkylwith 1 to 4 carbon atoms, a phenoxycarbonyl group which may besubstituted by at least one substituent selected from the classconsisting of a methyl group, a fluorine atom, a chlorine atom and abromine atom, a phenylthiocarbonyl group which may be substituted by atleast one substituent selected from the class consisting of a methylgroup, a fluorine atom, a chlorine atom and a bromine atom, abenzyloxycarbonyl group, a dimethylaminocarbonyl group, aphenylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom, and a bromine atom, abenzoylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chloride atom and a bromine atom, aphenylsulfonylaminocarbonyl group which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom and a bromine atom, a phenylthio group, an alkylsulfonylgroup which may be substituted by a fluorine atom and/or a chlorineatom, a phenylsulfonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom, a bromine atom and a nitro group, amethylcarbonylmethyl group, a phenacyl group which may be substituted bya fluorine atom and/or a chlorine atom, an organophosphono group, anorganothionophosphono group, --CH₂ --W or --CO--W,

W represents a 5 to 6 membered hetercyclic group, containing one or twohetero atoms selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by at leastone substituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom and alkyl groups having 1 to 4 carbonatoms,

R⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbonatoms, a phenyl group or a benzyl group,

Y represents a nitrogen atom or ##STR21## R⁹ represents a hydrogen atom,a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, analkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkylgroup having 1 to 4 carbon atoms which may be substituted by at leastone selected from the class consisting of a fluorine atom, a chlorineatom, a hydroxy group, an alkoxy group having 1 to 2 carbon atoms,alkylthio groups having 1 to 2 carbon atoms, a cyano group, adimethylamino group, alkylcarbonyl groups having an alkyl with 1 to 2carbon atoms and alkoxycarbonyl groups having an alkyl with 1 to 2carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a phenylgroup, an alkylcarbonyl group having an alkyl with 1 to 4 carbon atomswhich may be substituted by at least one selected from the classconsisting of a methoxy group, a chlorine atom and a fluorine atom, analkenylcarbonyl group having an alkenyl with 2 to 3 carbon atoms, abenzoyl group which may be substituted by at least one substituentselected from the class consisting of a fluorine atom, a chlorine atom,a bromine atom, a methoxy group and a methyl group, an alkoxycarbonylgroup which may be substituted by a fluorine atom and/or a chlorineatom, an alkylthiocarbonyl group having an alkyl with 1 to 4 carbonatoms, a phenoxycarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom, a bromine atom, a methyl group, a methoxy group and anitro group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, abenzoylaminocarbonyl group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom, aphenylsulfonylaminocarbonyl group which may be substituted by at leastone substituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom, analkylsulfonylaminocarbonyl group having an alkyl with 1 to 4 carbonatoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonylgroup which may be substituted by a fluorine atom and/or a chlorineatom, a phenylthio group which may be substituted by at least onesubstituent selected from the class consisting of a methyl group, afluorine atom, a chlorine atom and a bromine atom, or a phenylsulfonylgroup which may be substituted by at least one substituent selected fromthe class consisting of a methyl group, a fluorine atom, a chlorine atomand a bromine atom, in addition, R⁹ may form a bis-form of the formula(I), via a methylene group,

R represents a hydrogen atom or a methyl group, and

Z represents a 5 to 6 membered heterocyclic group, containing one tothree hetero atoms selected from the class consisting of an oxygen atom,a sulfur atom and a nitrogen atom, at least one of which is a nitrogenatom, which may be substituted by at least one substituent selected fromthe class consisting of a fluorine atom, a chlorine atom, a bromineatom, alkyl groups having 1 to 4 carbon atoms which may be substitutedby a fluorine atom and/or a chlorine atom, a nitro group, a cyano group,alkylsulfinyl group having 1 to 4 carbon atoms, alkylsulfonyl groupshaving 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atomswhich may be substituted by a fluorine atom and/or a chlorine atom,alkylthio groups having 1 to 4 carbon atoms which may be substituted bya fluorine atom and/or a chlorine atom, alkenyl groups having 2 to 3carbon atoms which may be substituted by a chlorine atom, an acetamidegroup which may be substituted by a fluorine atom and/or a chlorineatom, alkoxycarbonyl groups having an alkyl with 1 to 4 carbon atoms, athiocyanato group, alkynyl groups having 2 to 4 carbon atoms, an aminogroup, a methylamino group, a dimethylamino group, an acetyl group, aformyl group, a carboxy group, a hydroxy group, a mercapto group,cycloalkyl groups having 3 to 7 carbon atoms, an oxo group, a thioxogroup, alkenylthio groups substituted by a fluorine atom, a chlorineatom and/or a bromine atom, alkoxyalkyl groups having 2 to 4 carbonatoms in total, alkylaminocarbonyl groups having an alkyl with 1 to 2carbon atoms, dialkylaminocarbonyl groups having an alkyl with 1 to 2carbon atoms, a phenyl group, a phenoxy group and a benzyl group,provided that where R¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atomssimultaneously,

X represents ##STR22## and Y represents ##STR23## then Z must not standfor the pyridyl group.

Very particularly preferred heterocyclic compounds of the formula (I)are those in which

n represents 0 or 1,

R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or a methylgroup,

R³ and R⁴ independently represent a hydrogen atom or a methyl group,

X represents a sulfur atom, an oxygen atom or the following groups##STR24## R⁷ represents a hydrogen atom, an alkyl group which may besubstituted by at least one substituent selected from the classconsisting of a methoxy group, an ethoxy group, a methylthio group, anethylthio group, a cyano group, a fluorine atom, a chlorine atom and atrimethylsilyl group, an allyl group which may be substituted by achlorine atom, a propargyl group, a benzyl group which may besubstituted by a methyl group and/or a chlorine atom, a formyl group, avinylcarbonyl group, an alkylcarbonyl group having an alkyl with 1 to 3carbon atoms which may be substituted by at least one substituentselected from the class consisting of methoxy group, a phenoxy group anda chlorine atom, a benzoyl group which may be substituted by at leastone substituent selected from the class consisting of chlorine atom, abromine atom, a methyl group, a trifluoromethyl group, a methoxy groupand a nitro group, a benzylcarbonyl group which may be substituted by achlorine atom, an alkoxycarbonyl group having an alkyl with 1 to 2carbon atoms which may be substituted by a fluorine atom and/or achlorine atom, an alkylthiocarbonyl group having an alkyl with 1 to 2carbon atoms, a phenoxycarbonyl group which may be substituted by amethyl group and/or a chlorine atom, a phenylthiocarbonyl group whichmay be substituted by a chlorine atom, a benzyloxycarbonyl group, adimethylaminocarbonyl group, a phenylaminocarbonyl group, abenzoylaminocarbonyl group, a phenylsulfonylaminocarbonyl group whichmay be substituted by a methyl group and/or a chlorine atom, aphenylthio group, a methylsulphonyl group which may be substituted by achlorine atom, a phenylsulphonyl group which may be substituted by amethyl group, a methylcarbonylmethyl group, a phenacyl group which maybe substituted by a chlorine atom, O,O-diethylthionophosphone group,O-ethyl-S-n-propylthiolophosphone group, --CH₂ --W or --CO--W wherein p0W represents a 5 to 6 membered heterocyclic group, containing one or twohetero atoms selected from the class consisting of an oxygen atom, asulfur atom and a nitrogen atom, which may be substituted by a fluorineatom, a chlorine atom, a bromine atom and a methyl group,

R⁸ represents a hydrogen atom, a methyl group, a phenyl group or abenzyl group,

Y represents a nitrogen atom or ##STR25## R⁹ represents a hydrogen atom,a chlorine atom, a bromine atom, a hydroxy group, a methoxy group, abenzyloxy group, an alkyl group which may be substituted by at least onesubstituent selected from the class consisting of a fluorine atom, achlorine atom, a hydroxy group, a methoxy group, a cyano group, adimethylamino group, an acetyl group and a methoxycarbonyl group, anallyl group, a phenyl group, an acetyl group which may be substituted bya chlorine atom, a vinylcarbonyl group, an allylcarbonyl group, abenzoyl group, an alkoxycarbonyl group having an alkyl with 1 to 2carbon atoms which may be substituted by a fluorine atom,n-butylthiocarbonyl group, a phenoxycarbonyl group which may besubstituted by a chlorine atom and/or a methyl group, aphenylthiocarbonyl group, a benzyloxycarbonyl group, abenzoylaminocarbonyl group which may be substituted by a chlorine atom,a phenylsulfonylaminocarbonyl group which may be substituted by a methylgroup, a methylsulfonylaminocarbonyl group, a propylthio group, amethylsulphonyl group which may be substituted by a fluorine atom and/ora chlorine atom, a phenylthio group which may be substituted by achlorine atom, or a phenylsulphonyl group, in addition, R⁹ may form abis-form of the formula (I), via a methylene group, R represents ahydrogen atom or a methyl group, and

Z represents a 5 to 6 membered heterocyclic group, containing one tothree hetero atoms selected from the class consisting of an oxygen atom,a sulfur atom and a nitrogen atom, at least one of which is a nitrogenatom, which may be substituted by at least one substituent selected fromthe class consisting of a fluorine atom, chlorine atom, a bromine atom,a methyl group, fluoroalkyl groups having 1 to 2 carbon atoms, a methoxygroup, a methylthio group, a methylsulphinyl group, a methylsulphonylgroup, a nitro group, a cyano group, a trifluoromethoxy group, atrifluoromethylthio group, an allyl group, an acetyl group, a formylgroup and a carboxyl group, provided that where R¹, R², R³, R⁴, R⁵ andR⁶ represent hydrogen atoms simultaneously,

X represents ##STR26## and Y represents ##STR27## then Z must not standfor the pyridyl group.

Specifically, the following compounds may be mentioned:

3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazone,

3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(2-bromo-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-methyl-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-2-ethyl-5-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-2-ethyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydro-2H-1,3-thiazine,

3-(3-pyridylmethyl)-2-(nitromethylene) thiazolidine,

3-(3-pyridylmethyl)-2-(nitromethylene) tetrahydro-2H-1,3-thiazine,

3-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitromethylene) thiazolidine.

1-(5-pyrazolylmethyl)-2-nitromethylene)imidazolidine,

1-(5-chloro-1-methyl-3-pyrazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(3-trifluoromethyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(5-isoxazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-methyl-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-trifluoromethyl-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(1,2,3-thiadiazol-5-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-methyl-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitromethylene)imidazolidine,

1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitromethylene)imidazolidine,

1-(5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(5-pyrimidinylmethyl)-2-nitromethylene)imidazolidine,

1-(2-methyl-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-pyrazinylmethyl)-2-(nitromethylene)imdiazolidine,

1-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitromethylene)tetrahydropyrimidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-fluoro-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolifine,

1-(2-trifluoromethyl-5-pyrimidinylmethyl)-2-(nitromethylene)imidazolindine,

1-(2-chloro-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine,

1-[1-(2-fluoro-5-pyrimidinyl)ethyl]-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethtyl)-2-(nitroimino)tetrahydropyrimidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitroimino)tetrahydropyrimidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-fluoro-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-bromo-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-methyl-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-methoxy-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)pyrolidine,

1-(2-chloro-5-thiazolylmethyl)-2-(nitroimino)tetrahydropyrimidine,

1-(2-chloro-5-pyrimidinylmethyl)-2-(nitroimino)imidazolidene,

1-(2-chloro-5-pyrimidylmethyl)-4-methyl-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-3-(3-pyridylmethyl)-2-(nitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(bromonitromethylene)imidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-(1-nitro-2-oxopentylidene)imidazolidine,

ethyl nitro[3-(2-chloro-5-pyridylmethyl)thiazolidin-2-ylidene]acetate,

1-acetyl-3-(2-chloro-5-pyridylmethyl)-2-(nitroimino) imidazolidine, and

N-phenylsulfonyl-nitro[1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene]acetamide.

If, in the process (a), for example,N-(1-methyl-4-pyrazolymethyl)trimethylene diamine and1-nitro-2,2-bis(methylthio) ethylene are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR28##

If, in the process (b), for example, 2-(2-methyl-5-pyrazinylmethylamino)ethanethiol and 2,2-dichloronitroethylene are used as startingmaterials, the course of the reaction can be represented by thefollowing equation: ##STR29##

If, in the process (c), for example,2-(2-chloro-5-thiazolylmethylamino)ethanethiol and1,2,2,2-tetrachloro-1-nitroethane are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR30##

If, the process (d), for example,N-(2-chloro-5-pyridylmethyl)trimethylenediamine and nitroguanidine areused as starting materials, the course of the reaction can berepresented by the following equation: ##STR31##

If, in the process (e), for example,1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidine and fuming nitric acidare used as starting materials, the course of the reaction can berepresented by the following equation: ##STR32##

If, in the process (f), for example, 2-nitromethylenethiazolidine and2-chloro-5-pyridylmethylchloride are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR33##

The formula (II) provides a general definition of the compounds requiredas a starting material in the process (a), based on aforesaid eachdefinition of n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and X¹.

In the formula (II), n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and X¹ preferablyhave the meanings already given above.

The compounds of the formula (II) usable according to the inventioninclude both known and novel ones.

The known examples have already been described in, for instance,Japanese Patent Application Nos. 26,020/1984, 72,966/1984 and132,943/1984 Z. Anorg. Allgem. Chem., Vol. 312, pages 282-286, Khim.Geterotsikl. Soedin., 1974, No. 1, pages 122-123, Metody Poluch. Khim.Reactivon Prep., No. 17, pages 172-173, Issled. Obl. Geterotsikl.Soedin., 1971, pages 39-44, U.S. Pat. No. 4,018,931, Arch. Pharm., 1982,Vol. 315, pages 212-221, Metody Poluch. Khim. Reactivon Prep., 1967,pages 133-134, and Zh. Obshch Khim., Vol. 33, pages 1130-1135.

As examples, there may be mentioned the following:

N-(2-chloro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-5-pyridylmethyl)3-aminoethanethiol,

N-(2-bromo-5-pyridylmethyl)2-aminoethanethiol,

N-(2-bromo-5-pyridylmethyl)3-aminoethanethiol,

N-(2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-fluoro-5-pyridylmethyl)3-aminoethanethiol,

N-[1-(2-chloro-5-pyridyl)ethyl]2-aminoethanethiol,

N-2,3-dichloro-5-pyridylmethyl)2-aminoethanethiol,

N-(3-chloro-2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-4-pyridylmethyl)2-aminoethanethiol,

N-(3-chloro-2-pyridylmethyl)2-aminoethanethiol,

N-(5-chloro-2-pyridylmethyl)3-aminopropanethiol,

N-(3,5-dichloro-2-pyridylmethyl)2-aminoethanethiol,

N-(5-fluoro-2-pyridylmethyl)3-aminopropanethiol,

N-(6-bromo-2-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-pyridylmethyl)3-aminopropanethiol,

N-(5-chloro-3-pyridylmethyl)3-aminopropanethiol,

N-(5-bromo-3-pyridylmethyl)2-aminoethanethiol,

N-(5-fluoro-3-pyridylmethyl)2-aminoethanethiol,

N-[1-(2-fluoro-5-pyridyl)ethyl]2-aminoethanethiol,

N-(2,4-dichloro-5-pyridylmethyl)3-aminopropanethiol,

N-(2,4-dibromo-5-pyridylmethyl)2-aminoethanethiol,

N-(2,6-difluoro-4-pyridylmethyl)2-aminoethanethiol,

N-(2-fluoro-4-pyridylmethyl)3-aminopropanethiol,

N-(2,6-dibromo-4-pyridylmethyl)2-aminoethanethiol,

N-(3-bromo-2-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-fluoro-5-pyridylmethyl)2-aminoethanethiol,

N-[1-(2-chloro-5-pyridyl)propyl]2-aminoethanethiol,

N-(3-pyridylmethyl)2-aminoethanethiol,

N-(3-pyridylmethyl)3-aminopropanethiol,

N-(4-pyridylmethyl)2-aminoethanethiol,

N-(4-pyridylmethyl)3-aminopropanethiol,

N-(2-methyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-methyl-5-pyridylmethyl)3-aminopropanethiol,

N-(2-ethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-allyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-propargyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-methoxy-5-pyridylmethyl)3-aminopropanethiol,

N-(2-methylthio-5-pyridylmethyl)2-aminopropanethiol,

N-(2-methylsulfonyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-chloro-3-methyl-5-pyridylmethyl)2-aminoethanethiol,

N-[1-(3-pyridyl)ethyl]3-aminopropanethiol,

N-(2-trifluoromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethyl-5-pyridylmethyl)3-aminopropanethiol,

N-(2-nitro-5-pyridylmethyl)2-aminoethanethiol,

N-(2-nitro-5-pyridylmethyl)3-aminopropanethiol,

N-(2-cyano-5-pyridylmethyl)2-aminoethanethiol,

N-(2-cyano-5-pyridylmethyl)3-aminopropanethiol,

N-(2-methylsulfinyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-phenyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-benzyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-phenoxy-5-pyridylmethyl)3-aminopropanethiol,

N-(2-trichloromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2-ethoxyethyl)-5-pyridylmethyl]3-aminopropanethiol,

N-(2-methoxymethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-difluoromethoxy-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethoxy-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl]2-aminoethanethiol,

N-(2-chlorodifluoromethylthio-5-pyridylmethyl)3-aminopropanethiol,

N-(2-trifluoromethylthio-5-pyridylmethyl)2-aminoethanethiol,

N-(2-difluoromethyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethylsulfonyl-5-pyridylmethyl)2-aminoethanethiol,

N-(2-trifluoromethylsulfinyl-5-pyridylmethyl)2-aminoethanethiol,

N-[2-(2,2-dechlorovinyl)-5-pyridylmethyl)2-aminoethanethiol,

N-(4-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-4-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-6-oxo-1H,6H-dihydropyrimidin-4-ylmethyl)trimethylenediamine,

N-(5-pyrimidinylmethyl)ethylenediamine,

N-(2-methyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-dimethylamino-5-pyrimidinylmethyl)ethylenediamine,

N-(2-dimethylamino-5-pyrimidinylmethyl)trimethylenediamine,

N-(2,4,6-trichloro-5-pyrimidinylmethyl)ethylenediamine,

N-(pyrazinylmethyl)ethylenediamine,

N-[1-(pyrazinyl)ethyl]ethylenediamine,

N-(2-methyl-5-pyrazinylmethyl)ethylenediamine,

N-(3-pyridazinylmethyl)ethylenediamine,

N-(2-chloro-4-pyrimidinylmethyl)ethylenediamine,

N-(4-chloro-6-pyrimidinylmethyl)ethylenediamine,

N-(4-methyl-6-pyrimidinylmethyl)trimethylenediamine,

N-(2-fluoro-5-pyrimidinylmethyl)ethylenediamine,

N-[1-(2-fluoro-5-pyrimidinyl)ethyl]ethylenediamine,

N-(2-chloro-5-pyrimidinylmethyl)ethylenediamine,

N-(2-chloro-5-pyrimidinylmethyl)trimethylenediamine,

N-(2-isopropyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-chlorodifluoromethyl-5-pyridinylmethyl)ethylenediamine,

N-(2-trifluoromethyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-bromodifluoromethyl-5-pyrimidinylmethyl)ethylenediamine,

N-(2-methoxy-5-pyrimidinylmethyl)ethylenediamine,

N-(2-difluoromethoxy-5-pyrimidinylmethyl)ethylenediamine,

N-(2-trifluoromethoxy-5-pyrimidinylmetyl)ethylenediamine,

N-[2-(2,2,2-trifluoroethoxy)-5-pyrimidinylmethyl]trimethylenediamine,

N-(2-methylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-ethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-difluoroethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-(2-trifluoromethylthio-5-pyrimidinylmethyl)ethylenediamine,

N-[2-(2,2,2-trifluoroethylthio)-5-pyrimidinylmethyl)ethylenediamine,

N-(2-nitro-5-pyrazinylmethyl)ethylenediamine,

N-(2-cyano-5-pyrazinylmethyl)trimethylenediamine,

N-(2-chloro-5-pyrazinylmethyl)ethylenediamine,

N-(2-trifluoromethyl-5-pyrazinylmethyl)ethylenediamine,

N-(3-fluoro-6-pyridazinylmethyl)ethylenediamine,

N-(3-methyl-6-pyridazinylmethyl)trimethylenediamine,

N-(4-pyridazinylmethyl)ethylenediamine,

N-(3-chloro-6-pyridazinylmethyl)ethylenediamine,

N-(4-pyridazinylmethyl)trimethylenediamine,

N-(3-trifluoromethyl-6-pyridazinylmethyl)ethylenediamine,

N-(1,3,5-triazin-2-ylmethyl)ethylenediamine,

N-(3-chloro-1,2,4-triazin-6-ylmethyl)ethylenediamine,

N-(3,5-dichloro-1,2,4-triazin-6-ylmethyl)ethylenediamine,

N-(3-chloro-1,2,4,5-tetrazin-6-ylmethyl)ethylenediamine,

N-(3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(furfuryl)-ethylene(or -trimethylene)diamine,

N-(5-methylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(tetrahydrofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-methyltetrahydrofurfuryl)ethylene(or -trimethylene)diamine,

N-(3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-bromo-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyanofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylthio-2-thienylmethyl)-ethylene(or-trimethylene)diamine,

N-[1-(2-thienyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-5-isoazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-isothiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(1-methyl-4-pyrazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(1-ethyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-isopropyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-allyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-tert-butyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2,2,2-trifluoroethyl)-5-pyrazolylmethyl]-ethylene(or-trimethylene)diamine,

N-(3-methyl-5-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-methyl-5-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2,3,5-trimethyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-bromo-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-dichloro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,4-triazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-1,2,4-triazol-3-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,5-thiadiazol-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,2,3-thiadiazol-5ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-1,2,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,3-dioxolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-2-oxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-2-oxazolin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-ethyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-thienyl)-ethylene(or -trimethylene)diamine,

N-(1-ethyl-2-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-thienyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,5-dimethyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethyl-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethyl-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-chlorofurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-chlorofurufryl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-1-methyl-3-pyrrolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-bromo-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-nitrofufuryl)-ethylene(or -trimethylene)diamine,

N-(4-nitro-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-nitro-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-nitro-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-3-furylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-cyano-1-methyl-3-pyrrolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-difluoromethylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethyl-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-trifluoromethyl-3-pyrrolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-methoxy-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methylthiofurfuryl)-ethylene(or -trimethylene)diamine,

N-(2,5-dimethylthio-3-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethylthiofurfuryl)-ethylene(or -trimethylene)diamine,

N-[5-(2,2-dichlorovinyl)-2-thienylmethyl]-ethylene(or-trimethylene)diamine,

N-(5-ethoxycarbonylfurfuryl)-ethylene(or -trimethylene)diamine,

N-(5-formyl-2-thienylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isoxazlylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-ethyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isopropyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-fluoro-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-bromo-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-hydroxy-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-nitro-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-cyano-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-difluoromethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloromethyl-5-isoxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methoxymethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-isopropoxymethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-trichloromethyl-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-methoxy-5-isoazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethoxy-5-isoxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2,5-dimethyl-4-isoazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-isothiazolylmethylene)-ethylene(or -trimethylene)diamine,

N-(4-isothiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-pyrazoloylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-pyrazol)ethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-3-pyrazoloylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-pyrazoloylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-propyl-4-pyrazoloylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2,2,2-trifluoroethyl)-3-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-chloro-1-ethyl-3-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-chloro-1-isopropyl-3-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-1-methyl-3-pyrazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-trifluoromethyl-3-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-5-trifluoromethyl-3-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-3trifluoromethyl-5-pyrazoloylmethyl)-ethylene(or-trimethylene)diamine,

N-(4-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-oxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylthio-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-oxazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2,4-dimethyl-5-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-ethoxycarbonyl-2-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(5-thiazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-thiazolylmethyl]-ethylene(or -trimethylene)diamine,

N-[1-(2methyl-5-thiazolyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-ethyl-5-thiazolylmethyl]-ethylene(or -trimethylene)diamine,

N-(2-isopropyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-5-thiazolylmethyl)ethyl]-ethylene(or-trimethylene)diamine,

N-(2-nitro-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-nitro-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-mercapto-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chlorodifluoromethylthio-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2,2-trifluoroethylthio-5-thiazolylmethyl]-ethylene(or-trimethylene)diamine,

N-{2-[2-(2,3,3-trichloro)propenylthio]-5-thiazolylmethyl}-ethylene(or-trimethylene)diamine,

N-(2-thiocyanato-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-amino-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-acetamino-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-difluoromethoxy-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chloromethyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(1,1,2,2-tetrafluoroethyl)-5-thiazolylmethyl]ethylene(or-trimethylene)diamine,

N-(2-cyclopropyl-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-5-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-nitro-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-trifluoromethylthio-4-imidazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,2-dimethyl-4-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-2-trifluoromethyl-4-imidazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(1-methyl-1,2,3-triazol-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-methyl-1,2,3-triazol-4-yl)ethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-1,2,4-triazol-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-1,2,4-triazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(1,2,4-oxadiazol-5-ylmethyl)-ethylene(or trimethylene)diamine,

N-(1,3,4-oxadiazol-2-ylmethyl)-ethylene(or trimethylene)diamine,

N-(1,2,3-oxadiazol-5-ylmethyl)-ethylene(or trimethylene)diamine,

N-(3-trifluoromethyl-1,2,4-oxadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-methyl-1,3,4-oxadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-trifluoromethyl-1,3,4-oxadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-[2-(2,2,2-trifluoroethyl)-1,3,4-oxadiazol-5-ylmethyl]-ethylene(ortrimethylene)diamine,

N-(1,2,4-thiadiazol-5-ylmethyl)-ethylene(or trimethylene)diamine,

N-(1,2,3-thiadiazol-4-ylmethyl)-ethylene(or trimethylene)diamine,

N-[1-(1,2,3-thiadiazol-5-yl)ethyl]-ethylene(or trimethylene)diamine,

N-(1,3,4-thiadiazol-2-yl)-ethylene(or trimethylene)diamine,

N-[1-(1,3,4-thiadiazol-2-yl)ethyl]-ethylene(or trimethylene)diamine,

N-(1,2,5-thiadiazol-3-ylmethyl)-ethylene(or trimethylene)diamine,

N-(3-methyl-1,2,4-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(4-methyl-1,2,3-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-methyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-trifluoromethyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-fluoro-1,3,4-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(2-chloro-1,3,4-thiadiazol-5-ylmethyl)-ethylene(ortrimethylene)diamine,

N-(3-chloro-1,2,5-thiadiazol-4-ylmethyl)-ethylene(ortrimethylene)diamine,

N-[1-(3-tetrahydrofuryl)ethyl]-ethylene(or trimethylene)diamine,

N-(3-tetrahydrothienylmethyl]-ethylene or -trimethylene)diamine,

N-[1-(3-tetrahydrothienyl)ethyl]-ethylene or -trimethylene)diamine,

N-(1-methyl-3-pyrrolidinylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-oxathiolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-dioxolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-oxathiolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,3-dithiolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-1,3-dioxolan-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-1,3-oxathiolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chloromethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-trifluoromethyl-1,3-dioxolan-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-oxo-1,3-dioxolan-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-formyl-thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-acetyl-thiazolidin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,5-dihydrothiophen-2-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(1,1-dioxo-2,5-dihydrothiophen-3-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-isoxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-2-isoxazolin-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-trifluoromethyl-2-isoxazolin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-[3-(2,2,2-trifluoromethyl-2-isoxazolin-5-ylmethyl]-ethylene(or-trimethylene)diamine,

N-(2,4-dimethyl-2-oxazolin-4-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methyl-2-thiazolin-4-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-oxazolidinon-5-ylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-methyl-2-oxo-1,3-oxazolan-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoroacetamide-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-methyl-2-thioxo-thiazolidin-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-chloro-1,2,4-oxadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-carboxy-2-oxazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-dimethylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-phenoxyfurfuryl)-ethylene(or -trimethylene)diamine,

N-(1-phenyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-benzyl-4-pyrazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-phenyl-4-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(1-benzyl-2-imidazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfinyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylsulfonyl-5-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylthio-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-methylsulfonyl-1,3,4-thiadiazol-5-ylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-dimethylamino-5-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-carbamoyl-2-thiazolylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methylaminocarbonyl-2-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(5-dimethylaminocarbonyl-2-thiazolylmethyl)-ethylene(or-trimethylene)diamine,

N-(3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(3-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-[1-(3-pyridyl)propyl]-ethylene(or -trimethylene)diamine,

N-[2-methyl-1-(3-pyridyl)propyl]-ethylene(or -trimethylene)diamine,

N-(4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-5-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-nitro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-cyano-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-amino-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-acetamido-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-dimethylamino-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-ethoxycarbonyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-acetyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-difluoromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-trifluoromethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromodifluoromethyl-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-chlorodifluoromethyl-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(trichloromethyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(2-chloroethyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-[2-(2-fluoroethyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-[2-(2,2,2-trifluoroethyl)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(2-difluoroethoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-trifluoromethoxy-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2,2-trifluoroethoxy-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-[2-(trifluoromethylthio)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(2-formyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chlorodifluoromethylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-[2-(2,2-dichlorovinyl)-5-pyridylmethyl]-ethylene(or-trimethylene)diamine,

N-(5-trifluoromethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-ethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-butyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4,6-dimethyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3,5-dichloro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-bromo-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(5-ethyl-2-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(6-chloro-4-methyl-2-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-methyl-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-chloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-bromo-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromo-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(5-fluoro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-fluoro-5-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-[2-methyl-1-(2-fluoro-5-pyridyl)propyl]-ethylene(or-trimethylene)diamine,

N-(2-chloro-6-methyl-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-dichloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-dibromo-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,4-difluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methoxy-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-ethoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-isopropoxy-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylthio-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-methyl-2-methylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

N-(2-ethylthio-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfinyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methylsulfonyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(4-chloro-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(6-chloro-2-methyl-3-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-methyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-allyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-propargyl-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,3-dichloro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[2-(1-propenyl)-5-pyridylmethyl]-ethylene(or -trimethylene)diamine,

N-(2-chloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-fluoro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-methyl-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-[1-(2-chloro-4-pyridyl)ethyl]-ethylene(or -trimethylene)diamine,

N-(2-chloro-6-methyl-4-pyridylmethyl)-ethylene (or-trimethylene)diamine,

N-(2,6-dimethyl-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-bromo-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dibromo-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2,6-dichloro-4-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-bromo-2-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(2-chloro-3-fluoro-5-pyridylmethyl)-ethylene(or -trimethylene)diamine,

N-(3-chloro-2-methylthio-5-pyridylmethyl)-ethylene(or-trimethylene)diamine,

2-amino-1-(4-pyridylmethylamino)propane,

2-amino-2-methyl-(3-pyridylmethylamino)propane,

N-(4-pyridylmethyl)-2,2-dimethyltrimethylenediamine,

2-amino-1-(2-chloro-5-pyridylmethylamino)propane,

N-(2-chloro-5-pyridylmethyl)-2-methyltrimethylenediamine,

N-(3-pyridylmethyl)-N'-methylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N'-methylethylene (or-trimethylene)diamine,

N-(2-fluoro-5-pyridylmethyl)-N'-isopropylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N'-benzylethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N'-(3-pyridylmethyl)ethylenediamine,

N-(2-chloro-5-pyridylmethyl)-N'-(1-methyl-4-pyrazolylmethyl)ethylenediamine

2-methyl-2-(2-methyl-5-pyridylmethylamino)ethanethiol,

1-methyl-2-(2-chloro-5-pyridylmethylamino)ethanethiol,

2-(4-pyridylmethylamino)ethanol,

2-(3-pyridylmethylamino)ethanol,

3-(2-methyl-3-pyridylmethyl)propanol,

2-(2-methyl-5-pyridylmethyl)ethanol,

2-(2-chloro-5-pyridylmethyl)ethanol,

3-(2-trifluoromethyl-5-pyridylmethyl)propanol,

N-(1-methyl-4-pyrazolylmethyl)-2,2-dimethyltrimethylenediamine,

N,N'-bis-(5-methyl-2-furfuryl)ethylenediamine,

N-(3-methyl-5-isoxazolylmethyl)-N'-(1-methyl-4-pyrazolylmethyl)ethylene(or-trimethylene)diamine,

2-(3-methyl-5-isoxazolylmethylamine)ethanethiol,

3-(1-isopropyl-4-pyrazolylmethylamino)propanethiol,

2-(1,2,5-thiadiazol-3-ylmethylamino)ethanethiol,

2-(2-trifluoromethyl-5-thiazolylmethylamino)ethanethiol,

2-(3-methyl-5-isoxazolylmethylamino)ethanol,

2-(4-isothiazolylmethylamino)ethanol,

2-(5-oxazolylmethylamino)ethanol,

2-(3-trifluoromethyl-5-isoxazolylmethylamino)ethanol,

2-(5-pyrimidinylmethylamino)ethanethiol,

2-(3-trifluoromethyl-6-pyridazinylmethylamino)ethanethiol,

2-(2-methyl-5-pyridazinylmethylamino)ethanethiol,

2-(3-pyridazinylmethylamino)ethanol,

2-amino-1-(2-pyradinylmethyl)aminopropane,

N-(5-pyrimidinylmethyl)-N'-(1-methyl-4-pyrazolylmethyl)ethylenediamine,and

N-(3-chloro-6-pyridazinylmethyl)-N'-methylethylenediamine.

As aforesaid, the formula (II) includes a novel compounds.

In the case of the formula (II) having the following formula (IIa):##STR34## wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R and Z have the samemeanings as stated above,

X² represents an oxygen atom or ##STR35## R¹⁰ has the same meanings asstated above, the compounds of the formula (IIa) can be obtained when

(g) the compounds of the aforesaid formula (VIII) are reacted with thecompounds of the formula (IX) ##STR36## wherein n, R¹, R², R³, R⁴, R⁵,R⁶ and X² have the same meanings as stated above,

if appropriate, in the presence of inert solvents and in the presence ofacid acceptors.

If, in the process (g), for example, pyrazinylmethyl chloride andethylenediamine are used as starting materials, the course of thereaction can be represented by the following equation: ##STR37##

The compounds of the formula (II) can be obtained when

(h) the compounds of the formula (X) ##STR38## wherein Z and R have thesame meanings as stated above, are reacted with the compounds of theformula (XI) ##STR39## wherein n, R¹, R², R³, R⁴, R⁵, R⁶ and X¹ have thesame meanings as stated above,

and the resulting products are reduced, if appropriate, in the presenceof inert solvents.

If, in the process (h), for example, 6-chloronicotinealdehyde and3-aminopropanethiol are used as starting materials, the course of thereaction can be represented by the following equation: ##STR40##

In addition, if, the process (h), for example, 5-pyrimidinecarbaldehydeand ethylenediamine are used as the starting materials, the course ofthe reaction can be represented by the following equation: ##STR41##

The compounds of the formula (VIII), in the process (g), are the same asthe starting materials in the process (f), as mentioned hereinafter.

The compounds of the formula (IX) which include both known and novelones, can be easily produced by known processes.

As examples of the formula (IX), there may be mentioned:ethylenediamine, and trimethylenediamine. (see GermanOffenlegungsschrift 2,732,660 or French Patent no. 1,499,785).

There may also be mentioned 2-aminoethanol and 3-aminopropanole whichare well known compounds in organic chemistry.

In addition, N-benzyl-ethylene(or trimethylene) diamines [see JapaneseLaid-Open Patent Application No. 78,971/1985, German Offenlegungsschrift2,514,402, German Offenlegungsschrift 2,732,660 and Japanese PatentApplication No. 68,551/1985] and N-substituted alkyl-ethylene(ortrimethylene)diamines which correspond to ethylenediamines ortrimethylenediamines in the aforesaid formula (II) also included asexamples of the formula (IX).

In the practice of process (g), the desired compounds of the formula(II) can be easily obtained by reacting the compounds of formula (VII)with the compounds of formula (IX) in inert solvents such as illustratedin process (a) to be described in detail hereinbelow.

The process (g) can be easily carried out by using more than 1 mole, forexample about 5 moles, of the compounds of the formula (IX) per mole ofthe compounds of the formula (VIII) at a reaction temperature in therange of, for example, 0° to 50° C.

The compounds of the formula (X) used as the starting material inprocess (h) include for the most part known compounds.

As examples, there may be exemplified:

6-chloronicotinaldehyde,

6-bromonicotinaldehyde,

6-fluoronicotinaldehyde,

5-acetyl-2-chloropyridine,

5,6-dichloronicotinaldehyde,

5-chloro-6-fluoronicotinaldehyde,

2-chloro-4-pyridylcarbaldehyde,

3-chloro-2-pyridinecarbaldehyde,

3,5-dichloro-2-pyridinecarbaldehyde,

5-fluoro-2-pyridinecarbaldehyde,

6-bromo-2-pyridinecarbaldehyde,

2-chloronicotinaldehyde,

5-chloronicotinaldehyde,

5-bromonicotinaldehdye,

5-fluoronicotinaldehyde,

5-acetyl-2-fluoropyridine,

4,6-dichloronicotinaldehyde,

4,6-dibromonicotinaldehyde,

2,6-difluoro-4-pyridinecarbaldehyde,

2-fluoro-4-pyridinecarbaldehyde,

2,6-dibromo-4-pyridinecarbaldehyde,

5-bromo-6-fluoronicotinaldehyde,

6-chloro-5-fluoronicotinaldehyde,

2-chloro-5-propionylpyridine,

nicotinaldehdye,

4-pyridinecarbaldehyde,

6-methylnicotinaldehyde,

6-ethylnicotinaldehyde,

6-allylnicotinaldehyde,

6-propargylnicotinaldehyde,

6-methoxynicotinaldehdye,

6-methylthionicotinaldehyde,

6-methylsulfonylnicotinaldehyde,

6-chloro-4-methylnicotinaldehyde,

3-acetylpyridine,

6-nitronicotinaldehyde,

6-cyanonicotinaldehyde,

6-methylsulfinylnicotinaldehyde,

6-phenylnicotinaldehyde,

6-benzylnicrotinaldehyde,

6-phenoxynicotinaldehyde,

6-(2-ethoxyethyl)nicotinaldehyde,

6-trichloromethylnicotinaldehyde,

6-methoxymethylnicotinaldehyde,

6-difluoromethoxynicotinaldehyde,

6-trifluoromethoxynicotinaldehyde,

6-(2,2,2-trifluoroethoxy)nicotinaldehyde,

6-chlorodifluoromethylthionicotinaldehyde,

6-trifluoromethylthionicotinaldehyde,

6-difluoromethylnicotinaldehyde,

6-trifluoromethylsulfonylnicotinaldehyde,

6-trifluoromethylsulfinylnicotinaldehyde,

6-(2,2-dichlorovinyl)nicotinaldehyde,

4-pyrimidinecarbaldehyde,

2-methyl-4-pyrimidinecarbaldehyde,

2-methyl-6-oxo-1H,6H-dihydropyrimidine-4-carbaldehyde,

5-pyrimidinecarbaldehyde,

2-methyl-5-pyrimidinecarbaldehyde,

2-dimethylamino-5-pyrimidinecarbaldehyde,

2,4,6-trichloro-5-pyrimidinecarbaldehyde,

pyrazylcarbaldehyde,

acetylpyrazine,

2-methyl-5-pyrazinecarbaldehyde,

3-pyridazinecarbaldehyde,

2-chloro-4-pyrimidinecarbaldehyde,

4-chloro-6-pyrimidinecarbaldehyde,

4-methyl-6-pyrimidinecarbaldehyde,

2-fluoro-5-pyrimidinecarbaldehyde,

5-acetyl-2-fluoropyrimidine,

2-chloro-5-pyrimidinecarbaldehyde,

2-isopropyl-5-pyrimidinecarbaldehyde,

2-chlorodifluoromethyl-5-pyrimidinecarbaldehyde,

2-trifluoromethyl-5-pyrimidinecarbaldehyde,

2-bromodifluoromethyl-5-pyrimidinecarbaldehyde,

2-methoxy-5-pyrimidinecarbaldehyde,

2-difluoromethoxy-5-pyrimidinecarbaldehyde,

2-trifluoromethoxy-5-pyrimidinecarbaldehyde,

2-(2,2,2-trifluoroethoxy)-5-pyrimidinecarbaldehyde,

2-methylthio-5-pyrimidinecarbaldehyde,

2-ethylthio-5-pyrimidinecarbaldehyde,

2-difluoroethylthio-5-pyrimidinecarbaldehyde,

2-trifluoromethylthio-5-pyrimidinecarbaldehyde,

2-nitro-5-pyrazinecarbaldehyde,

2-cyano-5-pyrazinecarbaldehyde,

2-chloro-5-pyrazinecarbaldehyde,

2-trifluoromethyl-5-pyrazinecarbaldehyde,

3-fluoro-6-pyrazinecarbaldehyde,

3-methyl-6-pyrazinecarbaldehyde,

4-pyrazinecarbaldehyde,

3-chloro-6-pyrazinecarbaldehyde,

3-trifluoromethyl-6-pyrazinecarbaldehyde,

1,3,5-triazine-2-carbaldehyde,

3-chloro-1,2,4-triazine-6-carbaldehyde,

3,5-dichloro-1,2,4-triazine-6-carbaldehyde, and

3-chloro-1,2,4,5-tetrazine-6-carbaldehyde.

The compounds of the formula (X) can be produced according to variousconventional methods. They will be specifically described below.

For example, the pyridinecarbaldehydes of the formula (X) can beproduced by reacting the corresponding vinylpyridines according toozonolysis reaction (see J. org. chem., vol.26, 4912-4914) and inaccordance with British Patent No. 2,002,368, 6-chloronicotinaldehydecan be derived from 2-chloro-5-pyridylcarbonitrile.

In general, moreover, the formula (X) may be produced withoutdifficulty, according to a conventional method reducing thecorresponding carboxylic acids and the esters thereof or by theVilsmeyer reaction.

For example, pyridinecarbaldehydes also may be produced by reduction ofthe corresponding pyrdinecarboxylic acids and the esters thereof (seeOrg. React., vol.8, 218-257).

The formula (X) also may be directly prepared by ring formation. Forexample, with regards to 4-pyrimidinecarbaldehyde, the corresponding2-methylthio-4-methyl-6-pyrimidinecarbaldehyde acetal is obtained byreacting diethoxyacetylacetone with S-methylisothiourea. Subsequentreduction and treatment with hydrochloric acid give4-methyl-6-pyrimidinecarbaldehyde. The use of diethoxyacetylacetonederivatives in this reaction can lead to the synthesis of similarcompounds such as 4-pyrimidinecarbaldehyde,2-methyl-4-pyrimidinecarbaldehyde and2-trifluoromethyl-4-pyrimidinecarbaldehyde (described in Chem. Ber.,vol. 97, pages 3407-3417). Many known methods of synthesizing5-pyrimidinecarbaldehydes are known in the field of organic chemistry.

For example, 5-pyrimidinecarbaldehyde can be synthesized by introducinga formyl group into the 5-position of 4-hydroxy-6-oxodihydropyrimidineby the Vilsmeyer reaction, halogenating the product to form4,6-dichloro-5-formylpyrimidine, and then dehalogenating the resultingcompound (Liebigs Ann. Chem., vol. 766, pages 73-83; and Monatsh. Chem.,vol. 96, pages 1567-1572). By applying this reaction,2-alkyl-substituted and 2-haloalkyl-substituted5-pyrimidinecarbaldehydes can be synthesized. 5-pyrimidinecarbaldehydeshaving other substituents at the 2-position are described in JapaneseLaid-Open Patent Publication No. 59669/1984.

For example, 5-pyrimidinecarbaldehydes having substituents such asalkyl, alkoxy, alkylthio or alkylamino at the 2-position are obtained byreacting{2-[(dimethylamino)methylene]propanediylidene}bis[dimethylaminoperchlorate](describedin Collect. Czech. Chem. Comm., vol. 30, page 2125) with suitableamidine hydrochlorides.

As regards 5-pyrimidinecarbaldehydes having halogen at the 2-position,2-chloro-5-pyrimidinecarbaldehyde can be obtained, for example, bychlorinating ethyl 2-oxo-1,2-dihydro-5-pyrimidinecarboxylate withphosphorus oxychloride to obtain ethyl 2-chloro-5-pyrimidinecarboxylate(Chem. Pharm. Bull., vol. 12, pages 804-808; a similar example in J.Org. Chem., vol. 29, pages 1740-1743), and reducing the resultingcompound in a customary manner. Since the chlorine atom at the2-position has activity, it may be converted to another substituent suchas 2-fluoro by using potassium fluoride.

With regard to pyridazinecarbaldehydes, 3- and 4-pyridazinecarbaldehydesare described at page 213 of Monatsh. Chem., vol., 108, andmethyl-substituted pyridazinecarbaldehydes, in J. Heterocycle. Chem.,Vol. 17, page 1501.

Moreover, with regard to 5-membered heterocyclic-carbaldehydes, theywill be specifically described below. Furfural is a known compound, andcan easily permit introduction of a halogen atom into the furan ring.For example, 5-chlorofurfural and 4,5-dichlorofurfural can besynthesized from furfural (Zh. Org. Khim., Vol. 11, pages 1955-1958).5-Nitrofurfural is also an easily available known compound.5-Cyano-furfural is a compound described in Tetrahedron, Vol. 39, page3881, and 5-phenoxyfurfural is a compound described in Chem. Pharm.Bull., Vol. 28, No. 9, page 2846. Furancarbaldehydes other thanfurfural, alkyl-substituted, particularly methyl-substituted, furfuralsand other furancarbaldehydes are also known compounds and can be easilyobtained.

Thiophene carbonyl aldehyde is a known compound, and a halogen atom canbe easily introduced into the thiophene ring. For example,2,3-dichloro-4-thiophene carbaldehyde can be synthesized from3-thiophene carbaldehyde (Tetrahedron Vol, 32, pages 1403-1406).2,3-Dibromo-5-thiophene carbaldehyde can be synthesized from2-thiocarbaldehyde (J. Org. Chem., Vol, 41, page 2835).Alkyl-substituted, particularly methyl-substituted, thiophenecarbaldehydes are also known compounds. Alkylthio-substituted orhalogenalkylthio-substituted thiophenonecarbaldehydes can be obtained byalkylating or haloalkylating mercapto-substituted thiophenecarbaldehyde. For example, 2-methylthio-5-thiophenecarbaldehyde is aknown compound described in Zh. Obshch. Khim., Vol. 34, pages 4010-4015.Generally, alkylthio-substituted or halogenalkylthio-substitutedheterocyclic carbaldehydes can be synthesized by the above methods.

Nitro-substituted thiophenecarbaldehydes can easily be synthesized bynitration of the thiophene ring. For example,4-nitro-2-thiophenecarbaldehyde and 2-nitro-4-thiophenecarbaldehyde areknown compounds described in Bull. Soc. Chim. France, 1963, pages479-484.

Pyrrole carbaldehydes are known compounds. 1-Methyl-2-pyrrolecarbaldehyde can be synthesized from 1-methylpyrrole by the Vilsmeirreaction or by methylating 2-pyrrole carbaldehyde (Beilstein, Vol. 21,I, page 279).

4-iso-thiazole carbaldehyde can be synthesized from4-isothiazolylcarboxylic acid (J. Medicin. Chem., Vol. 13, pages1208-1212), and 5-isothiazole carbaldehyde can be synthesized from5-isothiazolyl lithium (J. Chem. Soc. 1964, pages 446-451).

5-Pyrazole carbaldehyde and 3-methyl-5-pyrazole carbaldehyde can besynthesized by direct ring synthesis (Chem. Ber., Vol. 97, pages3407-3417). By a similar method, 3-trifluoromethyl-5-pyrazolecarbaldehyde can be synthesized.

A formyl group can be introduced into the 4-position of an N-alkyl orN-aryl pyrazole by the Vilsmeyer reaction. 4-Pyrazole carbaldehyde canbe obtained by eliminating benzyl from N-benzyl-4-pyrazole carbaldehyde(J. Chem. Soc., 1957, pages 3314 and 1115).

4-Methyl-5-imidazole carbaldehyde and 1-methyl-5-imidazole carbaldehydeare known compounds (J. Pharm. Soc. Japan, Vol. 60, pages 184-188; J. A.C. S., Vol. 71, pages 2444-2448).

Many substituted thiazole carbaldehydes are known (Japanese Laid-OpenPatent Publication No. 206,370/1984; Chem. Ab., Vol. 62, 7764d; Chem.Ber., Vol. 101, page 3872). For example, 2-chlorothiazole-5-carbaldehydecan be synthesized by lithiation with butyllithium followed byformylation. Substituted 1,3,4-thiadiazole carbaldehydes are also knowncompounds (Japanese Laid-Open Patent Publication No. 206370/1984).1,2,3-Thiadiazole-5-carbaldehyde is also a known compound (BritishPatent No. 1,113,705).

The compounds of the formula (XI), in the process (h) encompass thecompounds of the aforesaid formula (IX).

In addition, as examples, 2-aminoethanethiol and 3-aminopropanethiol areexemplified (see J. Org. Chem., vol.27, 4712-4713) and theaminoalkanethiols, based on them, also may be included.

For example, in the case of X³ being a sulfur atom, the above process(h) can be carried out in the same way as described in J. Org. Chem.,vol.27, 2452-2457 and 4712-4713.

In carrying out the process (c), as first-step, the thiazolidines or thetetrahydrothiazines can be produced, as intermediate products, byreacting the compounds of the formula (X) with the compounds of theformula (XI) in the presence of inert solvent, such as benzene, and, asnext-step, the intermediates can be reduced by a reducing agent such assodium boron hydride, lithium aluminum hydride, aluminum boron hydride,potassium boron hydride, etc., to produce the compounds of the formula(IIb).

In carrying out the process (h) practically, the thiazolidines or thetetrahydrothiazines as intermediate products not only can be obtained bydistilling off volatile matter following the reaction of the first-step,under reduced pressure, for instance, 1 mmHg, at 50°-80° C., but alsocan be subjected to the reduction directly without the isolation.

In the case of X³ being ##STR42## according to process (h), the desiredcompound of the formula (IIb) can be obtained by heating the startingmaterials under reflux in an inert solvent (such as benzene), anddirectly reducing the reaction mixture in a customary manner withoutseparating the intermediate Schiff base or imine, as will bespecifically shown in a working example given hereinbelow.

In carrying out the process (h), more than 1 mole, for example about 5moles, of the compounds of the formula (XI) are used preferably per moleof the compounds of the formula (X), and the reaction is preferablycarried out under atmospheric pressure at a temperature of usually 0° to100° C.

Moreover, as an alternative process for the preparation of the formula(II) in which X¹ is a sulfur atom, there also may be cited a processwhich comprises halogenating the compounds of the formula (II) in whichX¹ is an oxygen atom by a halogenating agent such as thionylchloride,and thereafter reacting the resulting products with potassium hydrogensulfide.

The compounds of the formula (III), in the process (a), include bothknown and novel compounds.

As examples of known compounds, there may be mentioned: (for example,see Chem. Ber., vol.100, 591-604)

1-nitro-2,2-bis(methylthio)ethylene,

1-nitro-2,2-bis(ethylthio)ethylene,

1-nitro-2,2-bis(benzylthio)ethylene, and

2-nitromethylene-1,3-dithiolane.

The above compounds can be produced in a customary manner whichcomprises reacting nitromethane with carbon disulfide in the presence ofbase and alkylating the resulting product.

If other nitroalkanes are used in place of nitromethane in said process,similar compounds corresponding to the formula (III) may be producedeasily.

In addition, if the acyl-substituted nitromethanes are used in place ofnitromethane in said process, the desired formula (III) may be produced.

For example, if benzoylnitromethane is used,1-benzoyl-1-nitro-2,2-bismethylthioethylene, a novel compound, can beproduced, and if acetylnitromethane is used,1-acetyl-1-nitro-2,2-bis(methylthio)ethylene, a novel compound, can beproduced easily.

The compounds of the formula (IV), in the process (b), are known. (seeChem. Abst., vol.44, 1011F, Japanese Laid-Open Patent Application No.137,473/1984)

As examples, there may be mentioned:

2,2-dichloronitroethylene,

1,2,2-trichloronitroethylene,

1-fluoro-2,2-dichloronitroethylene,

1-methyl-2,2-dichloronitroethylene.

The compounds of the formula (V), in the process (c), are known. (see J.Org. Chem., vol.25, 1312, ibid, vol.28, 1281-1283, Chem. Ber. 75B,1324-1330, Japanese Laid-Open Patent Application No. 48,978/1985)

As examples, there may be mentioned:

2,2,2-trichloro-1-nitroethane,

1,2,2,2-tetrachloro-1-nitroethane,

2,2,2-trifluoro-1-nitroethane.

The formula (VI) provides a general definition of the compounds requiredas a starting material in the process (e), based on aforesaid eachdefinition of n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z.

In the formula (VI), n, R¹, R², R³, R⁴, R⁵, R⁶, X, R and Z preferablyhave the meanings already given above.

The compounds of the formula (VI) include both known and novel ones. Forexample, 2-imino-3-(4-pyridylmethyl) thiazolidine has been disclosed inJ. Med. Chem. vol.22, 237-247.

Other compounds of the formula (VI) also can be produced in the same wayas disclosed in the above reference.

The compounds of the formula (VI), for example, can be produced byreacting the aforesaid compounds of the formula (II) with cyanogenhalides.

Said reaction can be easily achieved by mixing the reactants withstirring in inert solvents, and the resulting products can be obtainedin the form of a hydrohalide.

As specific examples of the formula (VI) (in the form of a hydrohalide),there may be mentioned:

Hydrobromids or hydrochlorides of

1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-iminotetrahydropyrimidine,

1-(2-fluoro-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-bromo-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-trifluoromethyl-5-pyridylmethyl)-2-iminoimidazolidine,

1-(2-methyl-5-pyridylmethyl)-2-iminoimidazolidine,

1-(3-pyridylmethyl)-2-iminoimidazolidine,

1-(3-pyridylmethyl)-2-iminoimidazolidine,

1-(2-trifluoromethoxy-5-pyridylmethyl)-2-iminoimidazolidine, and

1-(2-methoxy-5-pyridylmethyl)-2-iminoimidazolidine.

The formula (VII) provides a general definition of the compoundsrequired as a starting material in the process (f), based on aforesaideach definition of n, R¹, R², R³, R⁴, R⁵, R⁶, X and Y.

In the formula (VII), n, R¹, R², R³, R⁴, R⁵, R⁶, X and Y preferably havethe meanings already given above.

The compounds of the formula (VII) are for the most part, known.

As examples, there may be mentioned:

2-nitromethyleneimidazolidine,

2-nitromethylenetetrahydropyrimidine,

4,4-dimethyl-2-nitrometyleneimidazolidine,

3-methyl-2-nitromethyleneimidazolidine,

3-allyl-2-nitromethyleneimidazolidine,

3-propargyl-2-nitromethyleneimidazolidine,

3-(3-chloroallyl)-2-nitromethyleneimidazolidine,

3-acetyl-2-nitromethyleneimidazolidine,

3-chloroacetyl-2-nitromethyleneimidazolidine,

3-benzoyl-2-nitromethyleneimidazolidine,

3-p-tosyl-2-nitromethyleneimidazolidine,

2-nitromethylenethiazolidine,

2-nitromethylene-tetrahydro-2H-1,3-thiazine,

2-nitromethylene-5-methylthiazolidine,

2-nitromethyleneoxazolidine,

2-nitromethylene-4-methyloxazolidine,

2-nitromethylene-tetrahydro-2H-1,3-oxazine,

2-nitromethylenepyrolidine,

2-nitromethylenepiperidine,

2-(1-nitroethylidene)imidazolidine,

2-(1-nitro-2-fluoroethylidene)imidazolidine,

2-(phenyl, nitromethylene)imidazolidine,

2-(1-nitro-2,2,2-trifluoroethylidene)imidazolidine,

ethyl nitro(imidazolidin-2-ylidene)acetate,

n-butyl nitro(tetrahydropyrimidin-2-ylidene)acetate,

o-tolyl nitro(imidazolidin-2-ylidene)acetate,

p-chlorophenyl nitro(imidazolidin-2-ylidene)acetate,

p-nitrophenyl nitro(imidazolidin-2-ylidene)acetate,

2-(methylthionitromethylene)imidazolidine,

2-(propylthionitromethylene)imidazolidine,

2-[(4-chlorophenylthio)nitromethylene)imidazolidine,

2-(acetylnitromethylene)imidazolidine,

2-(dinitromethylene)imidazolidine,

2-(benzoylnitromethylene)imidazolidine,

ethyl nitro(1-ethoxycarbonylimidazolidin-2-ylidene)acetate,

phenyl nitro(1-phenylthiocarbonylimidazolidin-2-ylidene)thiolacetate,

2-(phenylthionitromethylene)-1-phenylthioimidazolidine,

2-(1-nitroethylene)-tetrahydro-2H-1,3-thiazine,

2-(1-nitro-3-butynylidene)thiazolidine,

2-(1-nitro-3-butynylidene)-tetrahydro-2H-1,3-thiazine,

2-(1-nitro-2-phenylethylidene)thiazolidine,

2-(3-acetyl-1-nitropropylidene)-tetrahydro-2H-1,3-thiazine,

2-(3-cyano-1-nitropropylidene)-tetrahydro-2H-1,3-thiazine,

methyl 4-nitro-4-(thiazolidin-2-ylidene)butyrate,

2-(2-ethylthio-1-nitropropylidene)-tetrahydro-2H-1,3-thiazine,

2-(2-dimethylamino-1-nitroethylidene)thiazolidine,

ethyl nitro(tetrahydro-2H-1,3-thazin-2-ylidene)acetate,

phenyl nitro(tetrahydro-2H-1,3-thazin-2-ylidene)acetate,

2-formylnitromethylenethiazolidine,

2-acetylnitromethylene-tetrahydro-2H-1,3-thiazine,

2-benzoylnitromethylene-tetrahydro-2H-1,3-thiazine,

2-phenylthionitromethylene-tetrahydro-2H-1,3-thiazine,

ethyl nitro(oxazolidin-2-ylidene)acetate,

ethyl nitro(tetrahydro-2H-1,3-oxazin-2-ylidene)acetate,

3-methyl-2-nitromethylenepyrolidine,

3-fluoro-2-nitromethylenepyrolidine,

methyl nitro(pyrrolidin-2-ylidene)acetate,

3-methylthio-2-nitromethylenepiperidine,

ethyl nitro(thiazolidine-2-ylidene)acetate,

2-nitroiminoimidazolidine,

4,4-dimethyl-2-nitroiminoimidazolidine,

2-nitroiminotetrahydropyrimidine,

3-methyl-2-nitroiminoimiazolidine,

3-isopropyl-2-nitroiminoimiazolidine,

3-(2-ethoxyethyl)-2-nitroiminoimiazolidine,

3-ethoxycarbonyl-2-nitroiminoimiazolidine,

3-phenylthio-2-nitroiminoimiazolidine,

3-formyl-2-nitroiminoimiazolidine,

3-acetyl-2-nitroiminotetrahydropyrimidine,

3-(2-bromo-3,3-dimethylbutylyl)-2-nitroimidazolidine,

3-(2-trifluoromethylbenzoyl)-2-nitroiminoimidazolidine,

3-(2,4-dichloro-3-methylbenzoyl)-2-nitroiminoimidazolidine,

3-(4-methoxybenzoyl)-2-nitroiminoimidazolidine,

3-(3-chloropropylsulfonyl)-2-nitroiminoimidazolidine,

3-(2-difluoromethoxybenzoyl)-2-nitroiminotetrahydropyrimidine,

3-phenoxycarbonyl-2-nitroiminoimidazolidine,

3-(2-froyl)-2-nitroiminotetrahydropyrimidine,

3-(2-methylthiazol-5-ylcarbonyl)-2-nitroiminoimidazolidine,

3-(diethoxyphosphono)-2-nitoriminoimidazolidine,

3-(5-nitro-2-methylbenzenesulfonyl)-2-nitroiminoimidazolidine,

2-nitroiminothiazolidine,

2-nitroiminotetrahydro-2H-1,3-thiazine,

2-nitroiminooxazolidine,

4-methyl-2-nitroiminooxazolidine,

2-nitroiminopyrrolidine,

2-nitroiminopiperidine,

3-methyl-2-nitroiminopyrrolidine, and

2-nitroiminotetrahydro-2H-1,3-oxazine.

2-nitromethylene-imidazolidines (or tetrahydropyrimidines), of the abovesaid formula (VII), are known compounds (see, for instance, Chem. Ber.,vol.100, 591-604, Belgian Patent No. 821, 281, U.S. Pat. No. 3,971,774).

In addition, N-acyl derivatives from 2-nitromethyleneimidazolidines (ortetrahydropyrimidines) can be produced by known processes (see JapaneseLaid-Open Patent Application Nos. 67,473/1985 and 61,575/1985).

Moreover, in the case of another group, besides a nitro group, beingattached to the methylene group of 2-nitromethylene-imidazolidines (ortetrahydropyrimidines), said compounds of the formula (VII) can beproduced, in accordance with the known process described in U.S. Pat.Nos. 3,996,372, 4,002,765, 4,042,696, 4,052,411, 4,053,619, 4,053,622and 4,053,623 and Japanese Laid-Open Patent Application No. 151,727/1977and Belgian Patent No. 821,282.

2-nitromethylene-thiazolidines (or tetrahydro-2H-1,3-thiazines) arealso, for the most part, known compounds which can be easily produced,for instance, by reacting aminoalkanethiols with the aforesaid formula(III) that may be replaced by the aforesaid formula (IV) or formula (V).

Moreover, 2-position of 2-nitromethylene-thiazolidines (ortetrahydro-2H-1,3-thiazines) may be substituted by various knownprocesses to obtain desired starting materials of the formula (VII).(see U.S. Pat. Nos. 3,962,234, 4,022,775, 4,024,254, 4,044,128,4,045,434 and 4,076,813, and Japanese Laid-Open Patent Application No.151,882/1975).

2-nitromethylene-oxazolidines (or -tetrahydro-2H-1,3-oxazines) are alsoknown compounds which can be produced by reacting aminoalkanols with theaforesaid formula (III) that may be replaced by the aforesaid formula(IV) or formula (V). [see Adv. Pestic. Sci., Plenary Lect. Symp. Pap.Int. Congr. Pestic. Chem. 4-th, 1978, 206-217 (ref. Chem. abst., vol.91,103,654), U.S. Pat. No. 3,907,790, Japanese Laid-Open Patent ApplicationNos. 151,882/1975 and 151,727/1977].

2-nitromethylene-pyrrolidines (or piperidines) are also known compoundswhich, for example, can be produced by reacting 2-methoxypyrroline-1which nitroalkanes. (see Netherland Patent Nos. 7,306,020 and7,306,145).

2-nitroamino derivatives of the formula (VII) are also known compounds.

For instance, 2-nitroiminooxazolidines are described in J. Am. Chem.Soc., vol.73, 2213-2216.

2-nitroiminoimidazolidines, 2-nitroiminotetrahydropyrimidines andN-acetyl derivatives thereof are described in J. Am. Chem. Soc., vol.73,2201-2205 and British Patent No. 2,055,796.

N-acyl derivatives, excluding N-acetyl derivatives, N-sulfenylderivatives, N-sulfonyl derivatives and N-phosphono derivatives arenovel compounds which may be produced in the same way as described inBritish Patent No. 2,055,796.

2-nitroimino-thiazolidines (or tetrahydro-2H-1,3-thiazines,2-nitroimino-pyrrolidines or (piperidines) which can be produced byreacting nitroguanidine with the diamines, the aminoalkanols or theaminoalkanethiol, or by reacting 2-imino compound with nitric acid inthe presence of sulfuric acid, are also described in the aforesaidBritish Patent.

The formula (VIII) provides a general definition of the compoundsrequired as a starting material in the process (f), based on aforesaideach definition of Z and R.

In the formula (VIII), Z and R preferably have the meanings alreadygiven above.

The compounds of the formula (VIII) usable according to the inventioninclude known compounds, for instance, those already disclosed in J.Org. Chem., vol,34, 3547, J. Medicin. Chem., vol.14, 211-213 and557-558, 1971, U.S. Pat. No. 4,332,944, J. Heterocycl. Chem., 1979,vol.16, 333-337.

As examples, there may be mentioned:

3-picolyl chloride,

1-(3-pyridyl)ethyl chloride,

1-(3-pyridyl)propyl chloride,

2-methyl-1-(3-pyridyl)propyl chloride,

4-picolyl chloride,

5-chloro-2-pyridylmethyl chloride,

2-fluoro-5-pyridylmethyl chloride,

2-chloro-5-pyridylmethyl chloride,

1-(2-chloro-5-pyridyl)ethyl chloride,

2-nitro-5-pyridylmethyl chloride,

2-cyano-5-pyridylmethyl chloride,

2-amino-5-pyridylmethyl chloride,

2-acetamide-5-pyridylmethyl chloride,

2-dimethylamino-5-pyridylmethyl chloride,

2-ethoxycarbonyl-5-pyridylmethyl chloride,

2-acetyl-5-pyridylmethyl chloride,

2-chloro-3-methyl-5-pyridylmethyl chloride,

2-difluoromethyl-5-pyridylmethyl chloride,

5-trifluoromethyl-2-pyridylmethyl chloride,

2-bromodifluoromethyl-5-pyridylmethyl chloride,

2-chlorodifluoromethyl-5-pyridylmethyl chloride,

2-trichlormethyl-5-pyridylmethyl chloride,

2-(2-chloroethyl)-5-pyridylmethyl chloride,

2-(2-fluoroethyl)-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethyl)-5-pyridylmethyl chloride,

2-difluoromethoxy-5-pyridylmethyl chloride,

2-trifluoromethoxy-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl chloride,

2-(trifluoromethylthio)-5-pyridylmethyl chloride,

2-formyl-5-pyridylmethyl chloride,

2-chlorodifluoromethylthio-5-pyridylmethyl chloride,

2-(2,2-dichlorovinyl)-5-pyridylmethyl chloride,

5-trifluoromethyl-2-pyridylmethyl chloride,

5-methyl-2-pyridylmethyl chloride,

6-methyl-2-pyridylmethyl chloride,

4-methyl-2-pyridylmethyl chloride,

5-ethyl-2-pyridylmethyl chloride,

5-butyl-2-pyridylmethyl chloride,

4,6-dimethyl-2-pyridylmethyl chloride,

3-chloro-2-pyridylmethyl chloride,

3,5-dichloro-2-pyridylmethyl chloride,

5-fluoro-2-pyridylmethyl chloride,

6-bromo-2-pyridylmethyl chloride,

6-chloro-4-methyl-2-pyridylmethyl chloride,

5-methyl-3-pyridylmethyl chloride,

2-methyl-5-pyridylmethyl chloride,

2-chloro-3-pyridylmethyl chloride,

5-chloro-3-pyridylmethyl chloride,

5-bromo-3-pyridylmethyl chloride,

2-bromo-5-pyridylmethyl chloride,

5-fluoro-3-pyridylmethyl chloride,

2-fluoro-3-pyridylmethyl chloride,

1-(2-fluoro-5-pyridyl)ethyl chloride,

2-methyl-1-(2-fluoro-5-pyridyl)propyl chloride,

2-chloro-6-methyl-3-pyridylmethyl chloride,

2,4-dichloro-5-pyridylmethyl chloride,

2,6-dichloro-5-pyridylmethyl chloride,

2,4-dibromo-5-pyridylmethyl chloride,

2,4-difluoro-5-pyridylmethyl chloride,

2-methoxy-3-pyridylmethyl chloride,

2-methoxy-5-pyridylmethyl chloride,

2-ethoxy-5-pyridylmethyl chloride,

2-isopropoxy-5-pyridylmethyl chloride,

2-methylthio-3-pyridylmethyl chloride,

2-methylthio-5-pyridylmethyl chloride,

4-methyl-2-methylthio-5-pyridylmethyl chloride,

2-ethylthio-5-pyridylmethyl chloride,

2-methylsulfinyl-5-pyridylmethyl chloride,

2-methylsulfonyl-5-pyridylmethyl chloride,

4-chloro-2-fluoro-5-pyridylmethyl chloride,

6-chloro-2-methyl-3-pyridylmethyl chloride,

2-chloro-4-methyl-5-pyridylmethyl chloride,

2-allyl-5pyridylmethyl chloride,

2-propargyl-5pyridylmethyl chloride,

2,3-dichloro-5pyridylmethyl chloride,

2-(1-propenyl)-5pyridylmethyl chloride,

2-chloro-4-pyridylmethyl chloride,

2-fluoro-4-pyridylmethyl chloride,

2,6-dichloro-4-pyridylmethyl chloride,

2,6-difluoro-4-pyridylmethyl chloride,

2-methyl-4-pyridylmethyl chloride,

1-(2-chloro-4-pyridyl)ethyl chloride,

2-chloro-6-methyl-4-pyridylmethyl chloride,

2,6-dimethyl-4-pyridylmethyl chloride,

2-bromo-4-pyridylmethyl chloride,

2,6-dibromo-4-pyridylmethyl chloride,

3-chloro-2-fluoro-5-pyridylmethyl chloride,

3-bromo-2-fluoro-5-pyridylmethyl chloride,

2-chloro-3-fluoro-5-pyridylmethyl chloride,

3-chloro-2-methylthio-5-pyridylmethyl chloride,

2-ethyl-5-pyridylmethyl chloride,

2-phenyl-5-pyridylmethyl chloride,

2-benzyl-5-pyridylmethyl chloride,

2-phenoxy-5-pyridylmethyl chloride,

2-(2-ethoxyethyl)-5-pyridylmethyl chloride,

2-methoxymethyl-5-pyridylmethyl chloride,

2-difluoromethoxy-5-pyridylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyridylmethyl chloride,

2-trifluoromethylsulfonyl-5-pyridylmethyl chloride,

2-trifluoromethylsulfinyl-5-pyridylmethyl chloride,

3-furylmethyl chloride,

furfuryl chloride,

5-methylfurfuryl chloride,

2-thienylmethyl chloride,

4-imidazolylmethyl chloride,

4-methyl-5-imidazolylmethyl chloride,

tetrahydrofurfuryl chloride,

5-methyltetrahydrofurfuryl chloride,

3-thienylmethyl chloride,

2-pyrrolylmethyl chloride,

1-methyl-2-pyrrolylmethyl chloride,

5-methyl-2-thienylmethyl chloride,

5-bromo-2-thienylmethyl chloride,

5-cyanofurfuryl chloride,

5-trifluoromethylthio-2-thienylmethyl chloride,

1-(2-thienyl)ethyl chloride,

5-methyl-3-isoxazolylmethyl chloride,

5-isoxazolylmethyl chloride,

4-isoxazolylmethyl chloride,

3-methyl-5-isoxazolylmethyl chloride,

3-trifluoromethyl-5-isoxazolylmethyl chloride,

3-chloro-5-isoxazolylmethyl chloride,

5-isothiazolylmethyl chloride,

5-pyrazolylmethyl chloride,

4-pyrazolylmethyl chloride,

1-methyl-4-pyrazolylmethyl chloride,

1-(1-methyl-4-pyrazolyl)ethyl chloride,

1-ethyl-4-pyrazolylmethyl chloride,

1-isopropyl-4-pyrazolylmethyl chloride,

1-allyl-4-pyrazolylmethyl chloride,

1-tert-butyl-4-pyrazolylmethyl chloride,

1-(2,2,2-trifluoroethyl)-5-pyrazolylmethyl chloride,

3-methyl-5-pyrazolylmethyl chloride,

3-chloro-2-methyl-5-pyrazolylmethyl chloride,

2,3,5-trimethyl-4-pyrazolylmethyl chloride,

5-oxazolylmethyl chloride,

4-methyl-5-oxazolylmethyl chloride,

4-thiazolylmethyl chloride,

5-thiazolylmethyl chloride,

2-methyl-5-thiazolylmethyl chloride,

2-chloro-4-thiazolylmethyl chloride,

2-chloro-5-thiazolylmethyl chloride,

2-trifluoromethyl-5-thiazolylmethyl chloride,

2-bromo-5-thiazolylmethyl chloride,

2,4-dichloro-5-thiazolylmethyl chloride,

4-imidazolylmethyl chloride,

1-methyl-2-imidazolylmethyl chloride,

1,2,4-triazol-5-ylmethylchloride,

1-methyl-1,2,4-triazol-3-ylmethyl chloride,

1,2,5-thiadiazol-4-ylmethyl chloride,

1,2,3-thiadiazol-5-ylmethyl chloride,

3-methyl-1,2,4-oxadiazol-5-ylmethyl chloride,

1,3-dioxolan-2-ylmethyl chloride,

2,2-dimethyl-1,3-dioxolan-4-ylmethyl chloride,

2-methyl-2-oxazolin-5-ylmethyl chloride,

2-trifluoromethyl-2-oxazolin-5-ylmethyl chloride,

3-pyrrolylmethyl chloride,

1-ethyl-2-pyrrolylmethyl chloride,

1-methyl-3-pyrrolylmethyl chloride,

5-methyl-3-thienyl chloride,

5-methyl-3-pyrrolylmethyl chloride,

1,5-dimethyl-3-pyrrolylmethyl chloride,

2,5-dimethyl-3-furylmethyl chloride,

2,5-dimethyl-3-thienylmethyl chloride,

5-fluoro-3-furylmethyl chloride,

4-chlorofurfuryl chloride,

5-chlorofurfuryl chloride,

5-chloro-3-furylmethyl chloride,

5-chloro-1-methyl-3-pyrrolylmethyl chloride,

5-bromo-3-furylmethyl chloride,

5-nitrofurfuryl chloride,

4-nitro-2-thienylmethyl chloride,

5-nitro-2-thienylmethyl chloride,

1-methyl-5-nitro-3-pyrrolylmethyl chloride,

5-cyano-3-furylmethyl chloride,

5-cyano-3-thienylmethyl chloride,

5-cyano-1-methyl-3-pyrrolylmethyl chloride,

5-trifluoromethylfurfuryl chloride,

5-difluoromethylfurfuryl chloride,

5-trifluoromethyl-3-thienylmethyl chloride,

1-methyl-5-trifluoromethyl-3-pyrrolylmethyl chloride,

5-methoxy-2-thienylmethyl chloride,

5-methylfurfuryl chloride,

2,5-dimethylthio-3-thienylmethyl chloride,

5-trifluoromethylthiofurfuryl chloride,

5-(2,2-dichlorovinyl)-2-thienylmethyl chloride,

5-ethoxycarbonylfurfuryl chloride,

5-formyl-2-thienylmethyl chloride,

3-isoxazolylmethyl chloride,

4-isoxazolylmethyl chloride,

3-ethyl-5-isoxazolylmethyl chloride,

3-isopropyl-5-isoxazolylmethyl chloride,

3-fluoro-5-isoxazolylmethyl chloride,

3-bromo-5-isoxazolylmethyl chloride,

3-hydroxy-5-isoxazolylmethyl chloride,

3-nitro-5-isoxazolylmethyl chloride,

3-cyano-5-isoxazolylmethyl chloride,

3-difluoromethyl-5-isoxazolylmethyl chloride,

3-chlorodifluoromethyl-5-isoxazolylmethyl chloride,

3-methoxymethyl-5-isoxazolylmethyl chloride,

3-isopropoxymethyl-5-isoxazolylmethyl chloride,

3-trichloromethyl-5-isoxazolylmethyl chloride,

3-methoxy-5-isoxazolylmethyl chloride,

3-trifluoromethoxy-5-isoxazolylmethyl chloride,

3-methoxy-5-isoxazolylmethyl chloride,

3-trifluoromethoxy-5-isoxazolylmethyl chloride,

2,5-dimethyl-4-isoxazolylmethyl chloride,

3-isothiazolylmethyl chloride,

4-isothiazolylmethyl chloride,

3-pyrazolylmethyl chloride,

1-(4-pyrazolyl)ethyl chloride,

1-methyl-3-pyrazolylmethyl chloride,

1-methyl-5-pyrazolylmethyl chloride,

1-propyl-4-pyrazolylmethyl chloride,

1-(2,2,2-trifluoroethyl)-3-pyrazolylmethyl chloride,

5-chloro-1-ethyl-3-pyrazolylmethyl chloride,

5-chloro-1-isopropyl-3-pyrazolylmethyl chloride,

3-chloro-1-methyl-5-pyrazolylmethyl chloride,

5-trifluoromethyl-3-pyrazolylmethyl chloride,

1-methyl-5-trifluoromethyl-3-pyrazolylmethyl chloride,

1-methyl-3-trifluoromethyl-5-pyrazolylmethyl chloride,

4-oxazolylmethyl chloride,

2-methyl-4-oxazolylmethyl chloride,

2-methyl-5-oxazolylmethyl chloride,

2-fluoro-5-oxazolylmethyl chloride,

2-chloro-5-oxazolylmethyl chloride,

2-trifluoromethyl-5-oxazolylmethyl chloride,

2-methylthio-5-oxazolylmethyl chloride,

2-trifluoromethoxy-5-oxazolylmethyl chloride,

2,4-dimethyl-5-oxazolylmethyl chloride,

5-ethoxycarbonyl-2-oxazolylmethyl chloride,

1-(5-thiazolyl)ethyl chloride,

2-methyl-4-thiazolylmethyl chloride,

1-(2-methyl-5-thiazolyl)ethyl chloride,

2-ethyl-5-thiazolylmethyl chloride,

2-isopropyl-5-thiazolylmethyl chloride,

4-methyl-5-thiazolylmethyl chloride,

2-fluoro-4-thiazolylmethyl chloride,

2-fluoro-5-thiazolylmethyl chloride,

1-(2-chloro-5-thiazolyl)ethyl chloride,

2-nitro-4-thiazolylmethyl chloride,

2-nitro-5-thiazolylmethyl chloride,

2-cyano-4-thiazolylmethyl chloride,

2-cyano-5-thiazolylmethyl chloride,

2-methylthio-4-thiazolylmethyl chloride,

2-mercapto-5-thiazolylmethyl chloride,

2-methylthio-5-thiazolylmethyl chloride,

2-difluoromethylthio-5-thiazolylmethyl chloride,

2-trifluoromethylthio-5-thiazolylmethyl chloride,

2-chlorodifluoromethylthio-5-thiazolylmethyl chloride,

2-(2,2,2-trifluoroethylthio)-5-thiazolylmethyl chloride,

2-[2-(2,3,3-trichloro)propenylthio]-thiazolylmethyl chloride,

2-thiocyanato-5-thiazolylmethyl chloride,

2-amino-4-thiazolylmethyl chloride,

2-acetamino-4-thiazolylmethyl chloride,

2-methoxy-4-thiazolylmethyl chloride,

2-methoxy-5-thiazolylmethyl chloride,

2-trifluoromethoxy-5-thiazolylmethyl chloride,

2-difluoromethoxy-5-thiazolylmethyl chloride,

2-chloromethyl-5-thiazolylmethyl chloride,

2-difluoromethyl-5-thiazolylmethyl chloride,

2-trifluoromethyl-5-thiazolylmethyl chloride,

2-(1,1,2,2-tetrafluoroethyl)-5-thiazolylmethyl chloride,

2-cyclopropyl-5-thiazolylmethyl chloride,

2-imidazolylmethyl chloride,

1-methyl-5-imidazolylmethyl chloride,

2-fluoro-4-imidazolylmethyl chloride,

2-chloro-4-imidazolylmethyl chloride,

4-nitro-2-imidazolylmethyl chloride,

2-trifluoromethylthio-4-imidazolylmethyl chloride,

1,2-dimethyl-4-imidazolylmethyl chloride,

1-methyl-2-trifluoromethyl-4-imidazolylmethyl chloride,

1-methyl-1,2,3-triazol-4-ylmethyl chloride,

1-(1-methyl-1,2,3-triazol-4-yl)ethyl chloride,

3-methyl-1,2,4-triazol-5-ylmethyl chloride,

3-trifluoromethyl-1,2,4-triazol-5-ylmethyl chloride,

1,2,4-oxadiazol-5-ylmethyl chloride,

1,3,4-oxadiazol-2-ylmethyl chloride,

1,2,3-oxadiazol-5-ylmethyl chloride,

3-trifluoromethyl-1,2,4-oxadiazol-5-ylmethyl chloride,

2-methyl-1,3,4-oxadiazol-5-ylmethyl chloride,

2-trifluoromethyl-1,3,4-oxadiazol-5-ylmethyl chloride,

2-(2,2,2-trifluoroethyl)-1,3,4-oxadiazol-5-ylmethyl chloride,

1,2,4-thiadiazol-5-ylmethyl chloride,

1,2,3-thiadiazol-4-ylmethyl chloride,

1-(1,2,3-thiadiazol-5-yl)ethyl chloride,

1,3,4-thiadiazol-2-ylmethyl chloride,

1-(1,3,4-thiadiazol-2-yl)ethyl chloride,

1,2,5-thiadiazol-3-ylmethyl chloride,

3-methyl-1,2,4-thiadiazol-5-ylmethyl chloride,

4-methyl-1,2,3-thiadiazol-5-ylmethyl chloride,

2-methyl-1,3,4-thiadiazol-5-ylmethyl chloride,

2-trifluoromethyl-1,3,4-thiadiazol-5-ylmethyl chloride,

2-fluoro-1,3,4-thiadiazol-5-ylmethyl chloride,

2-chloro-1,3,4-thiadiazol-5-ylmethyl chloride,

3-chloro-1,2,5-thiadiazol-4-ylmethyl chloride,

1-(3-tetrahydrofuryl)ethyl chloride,

3-tetrahydrothienylmethyl chloride,

1-(3-tetrahydrothienyl)ethyl chloride,

1-methyl-3-pyrrolydinylmethyl chloride,

1,3-oxathiolan-2-ylmethyl chloride,

1,3-dioxolan-4-ylmethyl chloride,

1,3-oxathiolan-4-ylmethyl chloride,

1,3-dithiolan-4-ylmethyl chloride,

thiazolidin-5-ylmethyl chloride,

4-methyl-1,3-dioxolan-2-ylmethyl chloride,

2-methyl-1,3-oxathiolan-4-ylmethyl chloride,

2-chloromethyl-1,3-dioxolan-4-ylmethyl chloride,

2-trifluoromethyl-1,3-dioxolan-4-ylmethyl chloride,

2-oxo-1,3-dioxolan-4-ylmethyl chloride,

3-formyl-thiazolidin-5-ylmethyl chloride,

3-acetyl-thiazolidin-5-ylmethyl chloride,

3-thiolen-5-ylmethyl chloride,

2H,5H-1,1-dioxo-3-thiolen-3-ylmethyl chloride,

2-isoxazolin-5-ylmethyl chloride,

3-methyl-2-isoxazolin-5-ylmethyl chloride,

3-trifluoromethyl-2-isoxazolin-5-ylmethyl chloride,

3-(2,2,2-trifluoroethyl)-2-isoxazolin-5-ylmethyl chloride,

2,4-dimethyl-2-oxazolin-4-ylmethyl chloride,

2-methyl-1,3-thiazolin-4-ylmethyl chloride,

2-oxazolidon-5-ylmethyl chloride,

3-methyl-2-thiazolidinon-5-ylmethyl chloride,

2-methylamino-5-thiazolylmethyl chloride,

2-trifluoroacetamide-5-thiazolylmethyl chloride,

3-methyl-2-thioxo-thiazolidin-5-ylmethyl chloride,

3-chloro-1,2,4-oxadiazol-5-ylmethyl chloride,

5-carboxy-2-oxazolylmethyl chloride,

2-dimethylamino-5-thiazolylmethyl chloride,

5-phenoxyfurfuryl chloride,

1-phenyl-4-pyrazolylmethyl chloride,

1-benzyl-4-pyrazolylmethyl chloride,

2-phenyl-4-thiazolylmethyl chloride,

1-benzyl-2-imidazolylmethyl chloride,

2-methylsulfinyl-5-thiazolylmethyl chloride,

2-methylsulfonyl-5-thiazolylmethyl chloride,

2-carbamoyl-5-thiazolylmethyl chloride,

2-methylaminocarbonyl-5-thiazolylmethyl chloride,

2-dimethylaminocarbonyl-5-thiazolylmethyl chloride,

5-methylthio-1,3,4-thiadiazol-2-ylmethyl chloride,

5-methylsulfonyl-1,3,4-thiadiazol-2-ylmethyl chloride,

4-pyrimidinylmethyl chloride,

2-methyl-4-pyrimidinylmethyl chloride,

2-methyl-6-oxo-1H,6H-dihydropyrimidin-4-ylmethyl chloride,

5-pyrimidinylmethyl chloride,

2-methyl-5-pyrimidinylmethyl chloride,

2-dimethylamino-5-pyrimidinylmethyl chloride,

2,4,6-trichloro-5-pyrimidinylmethyl chloride,

pyrazinylmethyl chloride,

1-(pyrazinyl)ethyl chloride,

2-methyl-5-pyrazinylmethyl chloride,

3-pyridazinylmethyl chloride,

2-chloro-4-pyrimidinylmethyl chloride,

4-chloro-6-pyrimidinylmethyl chloride,

4-methyl-6-pyrimidinylmethyl chloride,

2-fluoro-5-pyrimidinylmethyl chloride,

1-(2-fluoro-5-pyrimidinyl)ethyl chloride,

2-chloro-5-pyrimidinylmethyl chloride,

2-isopropyl-5-pyrimidinylmethyl chloride, or bromide,

2-chlorodifluoromethyl-5-pyrimidinylmethyl chloride,

2-trifluoromethyl-5-pyrimidinylmethyl chloride,

2-bromodifluoromethyl-5-pyrimidinylmethyl chloride,

2-methoxy-5-pyrimidinylmethyl chloride,

2-difluoromethoxy-5-pyrimidinylmethyl chloride,

2-trifluoromethoxy-5-pyrimidinylmethyl chloride,

2-(2,2,2-trifluoroethoxy)-5-pyrimidinylmethyl chloride,

2-methylthio-5-pyrimidinylmethyl chloride,

2-ethylthio-5-pyrimidinylmethyl chloride,

2-difluoroethylthio-5-pyrimidinylmethyl chloride,

2-trifluoromethylthio-5-pyrimidinylmethyl chloride,

2-nitro-5-pyrazinylmethyl chloride,

2-cyano-5-pyrazinylmethyl chloride,

2-chloro-5-pyrazinylmethyl chloride,

2-trifluoromethyl-5-pyrazinylmethyl chloride,

3-fluoro-6-pyridazinylmethyl chloride,

3-methyl-6-pyridazinylmethyl chloride,

4-pyridazinylmethyl chloride,

3-chloro-6-pyridazinyl methyl chloride,

4-pyridazinylmethyl chloride,

3-trifluoromethyl-6-pyridazinylmethyl chloride,

1,3,5-triazin-2-ylmethyl chloride,

3-chloro-1,2,4-triazin-6-ylmethyl chloride,

3,5-dichloro-1,2,4-triazin-6-ylmethyl chloride, and

3-chloro-1,2,4,5-tetrazin-6-ylmethyl chloride.

In place of the chlorides hereinabove, the bromides or thep-toluensulfonates may also be exemplified. They will be specificallydescribed below.

The halides hereinabove, for instance the chlorides, can be producedwithout difficulty by chlorination of the corresponding alcohols withthionylchloride.

For instance, 2-chloro-5-pyridylmethylchloride can be obtained bychlorination of 2-chloro-5-pyridylmethylalcohol with thionylchloride.(see J. Org. Chem., vol. 34, 3547)

The bromides may also be produced by bromination of a methyl groupside-chain with N-bromosuccinimide.

Some of trifluoromethyl-substituted or trifluoromethoxy-substitutedpyridyl alcohols are described in J. Med. Chem., vol. 13, pages1124-1130. By using these synthesizing techniques,2-methyl-5-trifluoromethyl pyridine obtained by reaction of6-methylnicotinic acid with hydrofluoric acid and sulfur tetrafluorideis converted to an N-oxide, and the rearrangement reaction of theN-oxide can give 5-trifluoromethyl-2-pyridylmethyl alcohol.

This reaction can also be applied to the synthesis of5-methyl-2-trifluoromethylpyridine from 5-methylpicolic acid.2-Trifluoromethyl-5-pyridylmethyl bromide (or chloride), the desiredstarting substance, can be synthesized by monohalogenating the aforesaid5-methyl-2-trifluoromethylpyridine with N-bromosuccinimide orN-chlorosuccinimide.

2-Trifluoromethoxy-5-pyridylmethyl bromide (or chloride) can similarlybe obtained by reacting 5-methyl-2-trifluoromethoxypyridine obtainedfrom 2-hydroxy-5-methylpyridine, with N-bromosuccinimide orN-chlorosuccinimide.

Since the halogen at the ortho-position of the pyridine ring is active,a 2-haloalkoxy-5-pyridylmethyl alcohol can be synthesized, for example,by the reaction of 6-chloronicotinic acid with an excess of a sodiumalkoxide. Reduction of this compound can give the starting2-haloalkoxy-5-pyridylmethyl alcohol.

Halogenomethyl-substituted furans and thiophenes are known compounds.For example, 2-ethoxycarbonyl-5-chloromethylfuran is a known compounddescribed in Liebigs Annalen der Chemie, Vol. 580, page 176.2-Bromomethyl-5-trifluoromethylfuran is obtained by halogenating theside-chain of 2-methyl-5-trifluoromethylfuran with a halogenating agentsuch as N-bromosuccinimide (NBS) (U.S. Pat. No. 3,442,913).

Many bromomethyl-substituted heterocyclic compounds can be obtained bybrominating the corresponding methyl-substituted heterocyclic compoundswith N-bromosuccinimide.

Halogenomethyl-substituted isoxazoles can be obtained by halogenatingmethylisoxazole with NBS, etc. or hydroxymethyl isoxazole can be easilyconverted to chloromethyl isoxazole by thionyl chloride. For example,5-bromomethyl isoxazole is a compound described in GermanOffenlegungsschrift No. 2,716,687, and 4-bromomethylisoxazole is acompound described in Chem. Abst., Vol. 65, 2242 h.

Chloromethyl-substituted heterocyclic compounds can be synthesized bychloromethylation reaction. 4-Chloromethyl isoxazole and4-chloromethyl-3,5-dimethylisoxazole described in Zh. Obshch. Khim.,Vol. 34, pages 4010-4015 are good examples thereof. Furthermore,halogenomethyl-substituted isoxazoles can also be synthesized by directring synthesis. 3-Bromo-5-bromomethylisoxazole (Rend. Ist. Lombardo Sci.Pt. I. Classe Sci. Mat. e Nat., Vol. 94, pages 729-740, and5-bromomethyl-3-methylisoxazole (Japanese Laid-Open Patent PublicationNo. 59156/1988) are good examples thereof.

5-Chloromethyl-3-trifluoromethyl isoxazole can be obtained bysynthesizing 3-trifluoromethyl-5-hydroxymethyl isoxazole, andchlorinating it with thionyl chloride in accordance with the descriptionof Bull. Chem. Soc. Japan, Vol. 57, pages 2184-2187. The use of otherhalogenoalkyls instead of trifluoromethyl in the above reaction can leadto the synthesis of the corresponding halogenoalkyl isoxazoles. Asstated above, halogenoalkyl heterocyclic compounds can be easilyobtained generally by treating the corresponding alcohols withhalogenating agents typified by thionyl chloride.

5-Chloromethyl-3-hydroxyisoxazole is synthesized in accordance with thedescription of Tetrahedron Letters, 1965, No. 25, pages 2077-2079.Chlorination of it with phosphonyl chloride, etc., can give3-chloro-5-chloromethyl isoxazole.

Halogen-substituted halogenomethyl-substituted isothiazoles can beobtained, for example, by converting halogen-substitutedmethyl-substituted isothiazoles with halogenating agents such as NBSinto halogen-substituted bromomethyl-substituted isothiazoles.5-Bromo-3-bromomethylisothiazole (described in J. Chem. Soc., 1965,pages 7274-7276) is a good example.

4-Chloromethlpyrazole can be easily obtained by chlorinating4-hydroxymethylpyrazole with thionyl chloride (J. A. C. S., Vol. 71,pages 3994-4000).

As regards halogeno-halogenomethylpyrazoles,3-ethoxycarbonyl-5-hydroxy-1-methylpyrazole, for example, is synthesizedin accordance with the description of Chem. Pharm. Bull., Vol. 31, No.4, pages 1228-1234. Subsequent chlorination with phosphonyl chloridegives 5-chloro-1-methyl-3-pyrazolylcarbonyl chloride. Reduction of thechloride with sodium borohydride gives5-chloro-3-hydroxymethyl-1-methylpyrazole.

Chlorination of this product in a customary manner can give5-chloro-3-chloromethyl-1-methylpyrazole.

With regard to halogenomethyl-substituted oxazoles, chlorination ofhydroxymethyloxazole with thionyl chloride, etc., can give chloromethyloxazole. They can also by synthesized by direct ring synthesis.

For example, 5-bromomethyl-2-methyloxazole is a known compound (J. A. C.S., Vol. 104, pages 4461-4465) and 2-bromoethyl-5-ethoxycarbonyloxazoleis also a known compound (Japanese Laid-Open Patent Publication No.108771/1984).

4-Halogenomethylthiazoles can be directly synthesized, for example, byreacting dihalogenoacetones with thioacylamides such as thioacetamide(J. A. C. S., Vol. 56, pages 470-471, and ibid., Vol. 73, page 2936).

5-Halogenomethylthiazoles can be obtained by reacting a thioacylamidewith alpha-chloro-alpha-formylethyl acetate, reducing the resulting5-ethoxycarbonylthiazole with lithium aluminum hydride in a customarymanner, and halogenating the resulting 5-hydroxymethylthiazole.5-Chloromethyl-2-methylthiazole described in Zh. Obshch. Khim., Vol. 32,pages 570-575 and J. A. C. S., Vol. 104, pages 4461-4465 is a goodexample.

Reaction of thiourea instead of the thioacylamide can give2-amino-4-chloromethyl- or 2-amino-5-chloromethyl thiazole, and viadiazotization, a halogen atom, etc., can further be introduced. Thishalogen is active and can be converted to a 2-alkoxy group by a sodiumalkoxide (Japanese Laid-Open Patent Publication No. 5972/1979 and J.Chem. Soc., Perkin I, 1982, pages 159-162).

2-Halogeno-4- or 5-bromomethylthiazole can be synthesized by brominating2-halogeno-4- or 5- methylthiazoles with NBS.

The use of ammonium dithiocarbamate (Org. Synthesis, Coll, Vol. III,page 763) instead of the thioacetamide above can give 4- or5-halogenomethyl-2-mercaptothiazoles. Alkylation or haloalkylation cangive 2-alkylthio-4- or 5-halogenomethylthiazoles, or 2-substitutedalkylthio-4- or 5-halogenomethylthiazoles (J. A. C. S., Vol. 75, pages102-103).

A halogenomethyl imidazole, for example, chloromethylimidazole, can beobtained by hydroxymethylating an N-alkylimidazole with formaldehyde,optionally dealkylating it to form hydroxymethylimidazole, andchlorinating it with thionyl chloride, etc., in a customary manner(described in J. A. C. S., Vol. 71, pages 383-386).4-Hydroxymethylimidazole as one example of the hydroxymethyl imidazole,can be directly synthesized from fructose, formaldehyde and ammonia(described in Org. Synthesis Coll., Vol. III, page 460).

Hydroxymethyltriazole can be synthesized, for example, in accordancewith the procedure described in J. A. C. S., Vol. 77, pages 1538-1540,and chlorination of it can give chloromethyltriazole.

Halogenomethyloxadiazoles and halogenomethylthiazoles can be synthesizedrespectively by brominating methyl-substituted oxazole andmethyl-substituted thiazole with NBS. 3-Bromomethyl-1,2,5-thiadiazoledescribed in Japanese Laid-Open Patent Publication No. 24963/1974 and3-bromomethyl-4-chloro-1,2,5-thiadiazole are good example thereof. Thehalogenomethyl oxadiazoles and halogenomethylthiadiazoles can besynthesized by direct ring synthesis. For example,5-chloro-3-chloromethyl-1,2,4-thiadiazole described in J. Org. Chem,Vol. 27, pages 2589-2592, 3-chloro-5-chloromethyl-1,2,4-oxadiazoledescribed in West German OLS No. 2,054,342, and5-chloromethyl-3-methyl-1,2,4-oxadiazole described in Bull. Soc. Chim.Belges., Vol. 73, pages 793-798 are good examples thereof. The2-position substituted 5-chloromethyl-1,3,4-oxa(or thia)diazoledescribed in French Patent No. 1,373,290) is another good example.

Chloromethyl-substituted heterocyclic compounds can be synthesized byreducing carboxylic acids or ester derivatives thereof with lithiumaluminum hydride, etc. to convert them to alcohol derivatives, andfurther chlorinating the alcohol derivatives with thionyl chloride, etc.As examples thereof, Japanese Laid-Open Patent Publication No.89633/1984 describes 5-chloromethyl-1,2,3-thiadiazole,4-chloromethyl-1-methyl-1,2,3,5-tetrazole and4-chloromethyl-1-methyl-1,2,3-triazole.

Halogenoalkyl-substituted, saturated or partially unsaturatedheterocyclic compounds can be converted to chloromethyl-substitutedproducts by, for example, chlorinating their alcohol derivatives in acustomary manner.

Bromomethyldioxolane and bromomethyloxothiolane can be synthesized byreacting dimethyl bromoacetal with ethylene glycol, or reacting dimethylbromoacetal with 2-mercaptoethanol or reacting an aldehyde or ketonewith epibromohydrin. For example, 2-bromomethyl-1,3-dioxolane isdescribed in Beilstein, Vol. 19, II, page 8.

As regards chloromethyl-substituted oxazoline compounds,5-chloromethyl-3-methyl-2-isoxazoline can be synthesized in accordancewith the description of Pak. J. Sci. Res., Vol. 30, pages 91-94.5-Chloromethyl-3-trifluoromethyl- 2-isoxazoline may be synthesized bychlorinating 3-trifluoromethyl-5-hydroxymethyl-2-isoxazoline describedin Bull. Chem. Soc. Japan, Vol. 57, pages 2184-2187 in a customarymanner. 5-Chloromethyl-2-methyl-oxazoline is a compound described inTetrahedron, Vol. 34, pages 3537-3544.

4-Chloromethyl-2-methyl-2-thiazoline can be synthesized by chlorinating4-hydroxymethyl-2-methyl-2-thiazoline described in Heterocycles, Vol. 4,pages 1687-1692. 5-Chloromethyl-3-methyl-oxazolidin-2-one is a compounddescribed in West German OLS No. 1,932,219.3-Bromomethyl-1,1-dioxo-3-thiolene is a compound described in U.S. Pat.No. 4,561,764 and can be synthesized by bromination with NBS.

5-Pyrimidinylmethyl alcohol is obtained from 5-pyrimidinecarbaldehyde,and 2-chloro-5-pyrimidinylmethyl alcohol, from2-chloro-5-pyrimidinecarbaldehyde. 3-Pyridazinylmethyl alcohol can besynthesized from furfuryl acetate (Acta Chem. Scand., vol. 1, page 619).With regard to pyrazinyl alkyl halides, methylpyrazine ordimethylpyrazine which is easily available can be converted tochloromethylpyrazine by using N-chlorosuccinimide (Synthesis, 1984,pages 676-679). This reaction can be applied to methylpyrazines havingother substituents and halo-substituted methylpyridazines such as3-chloro-6-methylpyridazine (described in J. Chem. Soc., 1947, page242), and by this reaction 3-chloro-6-pyridazinylmethyl chloride can besynthesized. Furthermore, 2-chloro-5-pyrimidinylmethyl bromide can beobtained from 2-chloro-5-methylpyrimidine (Reacts. Sposobnost. Org.Soedin., vol. 5, pages 824-837) and N-bromosuccinimide.

As described in J. Hetrocycl. Chem., vol. 19, page 407 and Chem. Pharm.Bull., vol. 28, pages 3057 and 3063, ethyl2-chloropyrazine-5-carboxylate can be synthesized, and reduced to thecorresponding methanol (U.S. Pat. No. 2,910,824).

As regards triazinyl alkyl halides, 2,5-triazin-2-ylmethyl chloride, forexample, can be obtained by reacting 2-methyl-1,3,5-triazine withN-chlorosuccinimide (J. Org. Chem., vol. 29, pages 1527-1537).3,5-Dichloro-6-methyl-1,2,4-triazine (described in J. Med. Chem., vol.10, pages 883-887) and 3-chloro-6-methyl-1,2,4,5-tetrazine (J. Org.Chem., vol. 46, pages 5102-5109) can be chlorinated similarly byreacting with N-chlorosuccinimide.

In the formula (I) in which X is ##STR43## or Y is ##STR44## and whichcan be obtained by the above process (a), (b), (c), (d), (e) or (f),each hydrogen atom of the ##STR45## group and the ##STR46## groupthereof may be substituted by or added to other groups.

As specific examples, some compounds having active olefinic linkage,such as methylvinylketone, ethylacrylate, and acrylonitrile can bereacted with the ═CH-- group by Michael type addition. (see JapaneseLaid-Open Patent Application No. 151,882/1975)

Moreover, by Mannich reaction and others similar thereto, specifically,a dialkylaminomethyl group can be introduced to α-carbon atom of thenitromethylene group, and also active aldehydes such as formaldehyde andchloral may be added as well. (see Japanese Laid-Open Patent ApplicationNo. 151,882/1975)

In addition, each hydrogen atom of the above ##STR47## group and##STR48## group can also be halogenated by a halogenating agent such asN-chlorosuccinimide, N-bromosuccinimide, perchloryl fluoride and halogenper se. (see U.S. Pat. Nos. 3,933,809 and 3,962,233, Japanese Laid-OpenPatent Application No. 54,532/1974)

In the above cases, the formula (I) may have the following formula:##STR49## wherein n, R¹, R², R³, R⁴, R⁵, R⁶, R, Z and Hal have the samemeanings as stated above, and L represents a halogen atom, a phenylthiogroup or an alkoxycarbonyl group.

Glyoxalic acid and dimethylformaldehydedimethylacetal can also bereacted with α-carbon atom of the nitromethylene group, and said formula(I) may have the following formula: ##STR50## wherein n, R¹, R², R³, R⁴,R⁵, R⁶, R and Z have the same meanings as stated above.

The nitrogen atom of the above ##STR51## group and α-carbon atom of thenitromethylene group can independently be acylated, sulfenylated orsulfonylated. (see Netherland Patent No. 7,306,145, U.S. Pat. Nos.3,985,736, 3,996,372, 4,020,061, 4,022,775, 4,052,411, 4,053,662 and4,076,813).

Acylisocyanates and sulfonylisocyanates can be reacted with α-carbonatom of the nitromethylene group. (see U.S. Pat. Nos. 4,013,766,4,025,634, 4,029,791 and 4,034,091).

The nitrogen atom of the above ##STR52## group can also be alkylated(see Belgian Patent No. 821,282) and by using said reaction,third-position of the imidazolidines or the tetrahydropyrimidines can bealkylated to obtain the corresponding formula (I).

In carrying out the process (a), suitable diluents may be all inertorganic solvents.

Examples of such diluents include water; aliphatic, alicyclic andaromatic hydrocarbons (which may optionally be chlorinated) such ashexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,trichloroethylene and chlorobenzene; ethers such as diethyl ether,methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide,dioxane and tetrahydrofuran; nitriles such as acetonitrile,propionitrile and acrylonitrile; alcohols such as methanol, ethanol,isopropanol, butanol and ethylene glycol; acid amides such asdimethylformamide and dimethylacetamide; sulfones and sulfoxides such asdimethyl sulfoxide and sulfolane; and bases such as pyridine.

The process (a) can be carried out over a wide temperature range.Generally, it can be carried out at a temperature between about -20° C.and the boiling point of the mixture, preferably between about 50° C.and about 120° C. Desirably, the reaction is carried out under normalatmospheric pressure, but it is also possible to operate under elevatedor reduced pressures.

In the process (a), the desired novel compounds of the formula (I) canbe obtained, for example, by reacting the compounds of the formula (II)with 1 to about 1.2 moles, preferably 1 to about 1.1 moles, per mole ofthe compounds of the formula (II), of the compounds of the formula (III)in an inert solvent such as an alcohol (e.g., methanol or ethanol) untilthe generation of mercaptan ceases.

In carrying out the processes (b) and (c), suitable diluents may be theabove inert solvents exemplified for the process (a). As the base, forexample, hydroxides, carbonates, bicarbonates and alcoholates of alkalimetals, and testiary amines such as triethylamine, diethylamine andpyridine may also be cited.

The process (b) and (c) can be carried out over a broad temperaturerange, generally between about -20° C. and the boiling point of themixture, preferably between about 0° C. and about 50° C.

The reaction is carried out preferably under normal atmosphericpressure, but it is also possible to perform it under elevated orreduced pressure.

In the above processes (b) and (c), for example, about 1 to about 5moles preferably about 2 to about 4 moles, of a base and about 0.9 toabout 4 moles preferably about 1 to about 3 moles, of the compounds ofthe formulae (IV) or (V) can be used, per mole of the compounds of theformula (II).

In carrying out process (d), suitable diluents may be the above inertsolvents exemplified for the process (a).

According to process (d), the desired compounds of the formula (I) canbe easily obtained, for example, by reacting 1 mole of the compounds ofthe formula (II) with 1 to about 1.2 moles, preferably 1 to about 1.1moles, of nitroguanidine under heat in a water solvent.

The process (b) can be carried out at a temperature of, for example,about 0° C. to about 100° C., preferably about 30° C. to about 80° C.The reaction is preferably carried out under normal atmosphericpressure, but can also be carried out under elevated or reducedpressures.

In the practice of process (e), the compounds of the formula (VI) isusually dissolved in an acid such as conc. sulfuric acid prior to thereaction.

In carrying out the processes, the compounds of the formula (VI) andfuming nitric acid (with a purity of at least 98%) are reacted at lowtemperatures, preferably about 0° C. or lower to obtain the desiredcompounds of the formula (I) (by applying the method of British PatentApplication No. 2,055,796).

The compound of general formula (VI) used in the above process isgenerally present in the form of a hydrohalide as a result of itssynthesis as stated above, and usually it is neutralized in a customarymanner before using it in the process (e).

In the practice of the process (f), suitable diluents may be the aboveinert organic solvents exemplified for the process (a). As the bases,for example, hydrides such as sodium hydride and potassium hydride,hydroxides and carbonates of alkali metals may also be cited.

The process (f) can be carried out over a broad temperature range,generally between about 0° C. and about 100° C., preferably betweenabout 10° C. and about 80° C.

The reaction (f) is carried out preferably under normal atmosphericpressure, but it is also possible to perform it under elevated orreduced pressure.

In the process (f), the desired compounds of the formula (I) can beobtained, for example, by reacting the compounds of the formula (VII),in the presence of about 1.1 to 1.2 moles, per mole of the compound(VII), of sodium hydride as a base, with 1 to about 1.2 moles preferably1 to about 1.1 moles, per mole of the compound (VII), of the compoundsof the formula (VIII) in an inert solvent such as dimethylformamide. Inthe process (f), it is preferable for the reaction that the compound ofgeneral formula (VII) be converted in advance into its sodium salt byusing sodium hydride. In view of the characteristics of sodium hydride,such a reaction is desirably carried out under a nitrogen gasatmosphere.

The compounds of the formula (I) in accordance with this inventioninclude a tautomer as shown by the following formula.

In the case of X being NH and Y being CH, ##STR53##

In the case of X being NH and Y being N, ##STR54##

In addition, where Y is C--R⁹, the corresponding formula (I) may includeE,Z-isomer.

The compounds of the formula (I) may also be present in the form of asalt. Examples of the salt are inorganic acid salts, sulfonate salts,organic acid salts and metal salts.

The active compounds according to the invention exhibit powerfulinsecticidal effects.

They can, therefore, be used as insecticides. The active compounds canbe used for control and eradication of a wide range of pests, includingsucking insects, biting insects and other plant parasites, pests onstored grains and pests causing health hazards.

Examples of the pests are shown below.

Coleopterous insects

Callosobruchus chinensis,

Sitophilus zeamais,

Tribolium castaneus,

Epilachna vigitoctomaculata,

Agriotes fuscicollis,

Anomala rufocuprea,

Leptinotarsa decemkineata,

Diabrotica spp.,

Monochamus alternatus,

Lissorhoptrus oryzophilus, and

Lyctus brunneus.

Lepidopterous insects

Lymantria dispar,

Malacosoma neustria,

Pieris rapae,

Spodoptera litura,

Mamestra brssicae,

Chilo suppressalis,

Pyrausta nubilalis,

Ephestia cautella,

Adoxophyes orana,

Carpocapsa pomonella,

Agrotis fucosa,

Galleria mellonella,

Plutella maculipennis, and

Phyllocnistis citrella.

Hemipterous insects

Nephotettix cincticeps,

Nilaparvata lugens,

Pseudococcus cometocki,

Unaspis yanonensis,

Myzus persicae,

Aphis pomi,

Aphis gossypii,

Rhopalosiphum pseudobrassicas,

Stephanitis nashi,

Nazara spp.,

Cimex lextularius,

Trialeurodes vaporariorum, and

Psylla spp.

Orthopterous insects

Blatella germanica,

Periplaneta americana,

Cryllotalpa africana, and

Locusta migratoria migratoriodes.

Isopterous insects

Deucotermes speratus, and

Coptotermes formosanus.

Dipterous insects

Musca domestica,

Aedes aegypti,

Hylemia platura,

Culex pipens,

Anopheles sinensis, and

Culex tritaeniorhynchus.

In the field of veterinary medicine, the novel compounds of thisinvention are effective against various noxious animal parasites (endo-and ecto-parasites) such as insects and worms. Examples of such animalparasites are shown below.

Insects

Gastrophilus spp.,

Stomoxys spp.,

Trichodectes spp.,

Rhodnium spp., and

Ctenocephalides canis.

Substances having pesticidal activity against all of these pests maysometimes be referred to in this application simply as insecticides.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances, coatingcompositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans and fumigatingcoils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carries, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there by be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashyghly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs, or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agent are compounds which increase the action of theactive compounds, without it being necessary for the synergistic agentadded to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The following examples illustrate the present invention specifically. Itshould be noted, however, that the invention is not limited to themalone.

PREPARATIVE EXAMPLES Example 1 ##STR55##

A mixture of N-(2-chloro-5-pyridylmethyl)3-aminopropanethiol (4.3 g),1-nitro-2,2-bis(methylthio)ethylene (3.3 g) and ethanol (40 ml) washeated under reflux for 10 hours in a stream of nitrogen. After thereaction, about 2/3 of ethanol was distilled off under reduced pressure.Ether was added little by little to the reaction mixture to precipitatecrystals. The crystals were collected by filtration, and washed with amixture of ethanol and ether to give the desired3-(2-chloro-5-pyridymethyl)-2-nitromethylenetetrahydro-2H-1,3-thiazine(1.3 g) as yellow crystals.

m.p. 164°-166° C.

Example 2 ##STR56##

2-Nitromethylenethiazolidine (2.9 g) was dissolved in dry acetonitrile(30 ml), and 60% sodium hydride (0.9 g) was added at room temperature ina stream of nitrogen. Subsequently, the mixture was stirred at roomtemperature until the generation of hydrogen ceased. Then, a solution of2-chloro-5-pyridylmethyl chloride (3.2 g) in dry acetonitrile (5 ml) wasadded at room temperature, and the mixture was stirred at roomtemperature for 1 day. Acetonitrile was then distilled off under reducedpressure, and dichloromethane was added to the residue. The mixture wasthen washed with water. Dichloromethane was distilled off from thedichloromethane layer. The remaining oil was purified by silica gelcolumn chromatography to give the desired 3-(2-chloro-5-pyridylmethyl)-2-nitromethylenethiazolidine (1.6 g).

mp. 177°-179° C.

Example 3 ##STR57##

A mixture of N-(3-pyridylmethyl)3-aminopropanethiol (1.8 g),1-nitro-2,2-bis(methylthio)ethylene (1.7 g) and ethanol (40 ml) washeated under reflux for 5 hours under a nitrogen stream. After thereaction, about 2/3 by volume of ethanol was distilled off under reducedpressure. Ether was added little by little to the reaction mixture toprecipitate crystals. The crystals were collected by filtration, andwashed with a mixture of ethanol and ether to give the desired3-(3-pyridylmethyl)2-nitromethylenetetrahydro-2H-1,3-thiazine (1.2 g).

mp. 143°-146° C.

Example 4 ##STR58##

2-Nitromethylenethiazolidine (2.9 g) was suspended in dry acetonitrile(30 ml), and 60% sodium hydride (0.9 g) was added under a nitrogenstream. Then, the mixture was stirred at room temperature until thegeneration of hydrogen ceased. A solution of 3-picolyl chloride (3.2 g)in dry acetonitrile (5 ml) was added, and the mixture was stirred atroom temperature for 3 hours. Acetonitrile was distilled off underreduced pressure. Dichloromethane was added to the residue, and themixture was washed with water. Dichloromethane was then distilled offfrom the dichloromethane layer. The remaining oily product was purifiedby column chromatography to give the desired3-(3-pyridylmethyl)2-nitromethylenethiazolidine (0.5 g).

mp. 96°-100° C.

Example 5 ##STR59##

A mixture of 16.8 g ofN-(1-methyl-4-pyrazolylmethyl)-trimethylenediamine, 16.5 g of1-nitro-2,2-bis(methylthio)ethylene and 200 ml of ethanol was heatedunder reflux until the generation of methylmercaptan ceased. The mixturewas cooled, and the precipitated crystals were collected by filtration.Washing with methanol gave 16.6 g of the desired1-(1-methyl-4-pyrazolylmethyl)2-(nitromethylene)tetrahydropyrimidine aspale yellow crystals.

mp. 186°-190° C.

Example 6 ##STR60##

A mixture of 15.5 g of N-(3-methyl-5-isoxazolylmethyl)-ethylenediamine,16.5 g of 1-nitro-2,2-bis(methylthio)ethylene and 200 ml of ethanol washeated under reflux until the generation of methylmercaptan ceased. Theperiod of about 3 hours was required. Then, the reaction mixture wascooled to room temperature, whereupon the desired product precipitatedas crystals. The crystals were collected by filtration and washed withethanol to give 12.5 g of1-(3-methyl-5-isoxazolylmethyl)2-(nitromethylene)imidazolidine as yellowcrystals.

mp. 168°-170° C.

Example 7 ##STR61##

2-Nitromethylene imidazolidine (12.9 g) was dissolved in 60 ml of drydimethylformamide, and 4.4 g of 60% sodium hydride was added little bylittle in a nitrogen stream at room temperature, and successively, themixture was stirred at room temperature to 30° C. for 3 hours to formthe sodium salt of the imidazolidine compound. Then, 11.8 g of5-isoxazolylmethyl chloride was added at room temperature, and themixture was stirred at room temperature for 24 hrs. The reaction mixturewas carefully poured into 150 ml of ice water and extracted twice withdichloromethane. Dichloromethane was distilled off from thedichloromethane layers to give 12 g of the desired1-(5-isoxazolylmethyl)2-(nitromethylene)imidazolidine as brown crystals.

mp. 156°-158° C.

Example 8 ##STR62##

N-(2-Methyl-5-thiazolylmethyl)trimethylenediamine (18.5 g) was dissolvedin 100 ml of acetonitrile, and 1-nitro-2,2-bis(methylthio)ethylene (16.5g) was added. With stirring, the mixture was refluxed for 6 hours. Afterthe reaction, the reaction mixture was cooled to room temperature. Theresulting crystals were collected by filtration and washed with methanolto give 10.2 g of the desired1-(2-methyl-5-thiazolylmethyl)2-(nitromethylene)tetrahydropyrimidine.

mp. 204°-207° C.

Example 9 ##STR63##

A mixture of 2-fluoro-5-pyridylmethyl bromide (9.5 g),2-(nitroimino)imidazolidine (6.5 g), potassium carbonate (7.6 g) andacetonitrile (100 ml) was refluxed for 2 hours with stirring. After thereaction, the reaction mixture was cooled to room temperature, and coldwater (100 ml) was added. The resulting crystals were collected byfiltration and washed with ether to give slightly colored1-(2-fluoro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (6.0 g) as thedesired compound.

mp. 121°-124° C.

Example 10 ##STR64##

A solution composed of N-(2-chloro-5-pyridylmethyl)trimethylenediamine(10 g), nitroguanidine (5.7 g) and water (80 ml) was heated at 80° C.for 3 hours. The reaction mixture was cooled to room temperature, andextracted twice with 50 ml of dichloromethane. Dichloromethane wasdistilled off from the extracts, and the tarry residue was purified bysilica gel column chromatography to give almost colorless1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)tetrahydropyrimidine (6.1 g).

mp. 113°-117° C.

Example 11-i ##STR65##

A solution of N-(2-chloro-5-pyridylmethyl)ethylenediamine (18.6 g) intoluene (200 ml) was stirred at room temperature, and cyanogen bromide(10.6 g) was added portionwise. Then, the mixture was further stirred.Since the desired 1-(2-chloro-5-pyridylmethyl)-2-iminoimidazolidineprecipitated as a hydrobromide, the reaction mixture was filtered andthe filtrate was washed with ether.

mp. 202°-205° C.

Example 11-ii ##STR66##

The hydrobromide (5.8 g) synthesized in Example 11-i was added to 98%sulfuric acid (30 ml) at 0° C. Then, with stirring, 2 ml of fumingnitric acid was added dropwise at 0° C. After the addition, the mixturewas stirred at 0° C. for 2 hours. The reaction mixture was poured intoice water (100 g) and extracted with dichloromethane. Dichloromethanewas distilled off from the extract under reduced pressure to give paleyellow crystals. The crystals were washed with ether to give1(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (1.5 g).

mp. 136°-139° C.

Example 12 ##STR67##

Sodium hydride (0.48 g) was added to a solution of2,2,2-trifluoroethanol (2.4 g) in toluene (30 ml) was added, and themixture was stirred until the generation of hydrogen ceased. As aresult, 2,2,2-trifluoroethanol sodium salt was prepared. To the productwere added 1-(2-chloro-5-pyridylmethyl)-2-(nitroimino)imidazolidine (5.1g) synthesized by the method of Example 3 and a catalytic amount of4-dimethylaminopyridine. The mixture was heated at 80° C. for 10 hourswith stirring. After cooling the reaction mixture, the precipitatedcrystals were collected by filtration, washed with water and ether andthen purified by silica gel chromatography to give1-[2-(2,2,-trifluoroethoxy)-5-pyridylmethyl]-2-(nitroimino)imidazolidine(1.5 g).

mp. 109°-112° C.

Example 13 ##STR68##

A mixture of N-(5-pyrimidinylmethyl)ethylenediamine (15.2 g),1-nitro-2,2-bis(methylthio)ethylene (14.9 g) and ethanol (100 g) wasrefluxed with stirring until the generation of methylmercaptan ceased(for about 3 hours). The reaction mixture was cooled to roomtemperature, and the resultant crystals were collected by filtration.The crystals were washed with ethanol, and dried to give1-(5-pyriminidinylmethyl)-2-(nitromethylene)imidazolidine (12.7 g) aspale yellow crystals. This product decomposes at 236° C.

Example 14 ##STR69##

2-Nitromethyleneimidazolidine (12.9 g) was dissolved in drydimethylformamide (100 ml), and at room temperature 60% oily sodiumhydride (4.4 g) was added. The mixture was stirred at room temperatureuntil the generation of hydrogen ceased. Then 2-methyl-5-pyrazinylmethylchloride (14.3 g) was added at room temperature, and the mixture wasstirred at 40° C. for 8 hours. After cooling to room temperature, thereaction mixture was added to 200 ml of water, and extracted withdichloromethane. On distilling off dichloromethane from the organiclayer under reduced pressure,1-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)imidazolidine (5.4 g)was obtained as yellow crystals having a melting point of 163° to 166°C.

Example 15 ##STR70##

A mixture of 2 g of 2-amino-1-(2-chloro-5-pyridylmethylamino)propane,1.6 g of 1-nitro-2,2-bis (methylthio)ethylene and 20 ml of methanol wasrefluxed for 5 hours with stirring. A crystaline product wasprecipitated after standing at room temperature. The product wasfiltered with suction, washed with methanol and then dried in vacuum.1.9 g of1-(2-chloro-5-pyridylmethyl)-4-methyl-2-(nitromethylene)imidazolidinewas obtained in form of light yellow crystals.

mp. 170°-174° C.

Example 16 ##STR71##

A mixture of 2.6 g ofN-(3-methyl-5-isoxazolylmethyl)-N'-(1-methyl-4-pyrazolylmethyl)trimethylenediamine,1.6 g of 1-nitro 2,2-bis(methylthio)ethylene and 10 ml of ethanol wasrefluxed for 15 hours with stirring. After the reaction, the ethanol wasremoved by vacuum distillation. The tarry residue was purified bychromatography on a silicagel column. The product, 0.7 g of1-(3-methyl-5-isoxazolylmethyl-3-(1-methyl-4-pyrazolylmethyl)-2-(nitromethylene)tetrahydropyrimidinewas obtained as a viscous oil.

n_(D) ²⁰ 1.5670.

Example 17 ##STR72##

6.6 g of finely powdered 1-nitro-2,2-bis(methylthio) ethylene was wellmixed with 7.5 g of 2-(2-chloro-5-pyridylmethylamino)ethanol. Themixture was heated to 110°-120° C. for 30 minutes or until thegeneration of methylmercaptan is ceased. The resulting oil was cooled toroom temperature and purified by chromatography on a silicagel column.The product 3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)oxazolidineweighed 1.7 g.

mp. 123°-124° C.

Example 18 ##STR73##

2.6 g of potassium hydroxide was dissolved in 20 ml of anhydrousethanol. To the solution, were added 3.7 g of2-(2-methyl-5-pyrazinylmethylamino)ethanethiol under nitrogenatmosphere. The solution was then cooled to 0° C., and 3.0 g of2,2-dichloro-1-nitroethylene was added dropwise at 0°-10° C. After theaddition, the mixture was stirred for 1 hour at 10° C. The ethanol wasremoved by vacuum distillation, chloroform was added to the residue andthe chloroform layer was washed with 1% of sodium hydroxide solution andwater. The chloroform layer was treated by usual manner, light yellowcrystals of3-(2-methyl-5-pyrazinylmethyl)-2-(nitromethylene)thiazolidine wereobtained, and weighted 2.0 g.

mp. 147°-150° C.

Example 19 ##STR74##

A mixture of 4.7 g of N-(1,2,5-thiadiazol-3-ylmethyl)ethylenediamine,3.4 g of nitroguanidine and 20 ml of water was stirred at 50°-60° C. for1 hour then at 70° C. for 20 minutes. The resulting solution was thencooled slowly to 5° C., and the product was precipitated. Thecrystalline product was collected by filtration washed with water andmethanol, and dried. The yield of1-(1,2,5-thiadiazol-3-ylmethyl)-2-(nitroimino)imidazolidine was 2.9 g.

mp. 162°-165° C.

Example 20 ##STR75##

A mixture of 2.9 g of 2-nitroiminothiazolidine, 2.9 g of anhydrouspotassium carbonate, 3.2 g of 2-chloro-5-pyridylmethylchloride and 50 mlof acetonitrile was refluxed for 5 hours with vigorously stirring. Afterthe reaction, most of the acetonitrile was removed by distillation andwater was added to the residue. As the solid product was separated, itwas collected by filtration. The crude material was recrystallized fromethanol to give desired3-(2-chloro-5-pyridylmethyl)-2-(nitroimino)thiazolidine.

yield 3.8 g.

mp. 137°-138° C.

Example 21 ##STR76##

To a mixture of 1.3 g of finely powdered 2-nitroiminoimidazolidine and30 ml of dry acetonitrile was added portionwise 0.4 g of sodium hydride(60% in oil) at room temperature and was stirred until the generation ofhydrogen gas ceased. A solution of 1.7 g of2-chloro-5-thiazolylmethylchloride in 10 ml of acetonitrile was thenadded dropwise at room temperature. After the addition, the mixture wasstirred for 3 hours at room temperature and poured onto ice water. Theorganic layer was extracted with dichloromethane and the dichloromethaneextract was washed with 1% sodium hydroxide solution and water. Theproduct was solidified after evaporation of dichloromethane, washed withether and dried. The desired1-(2-chloro-5-thiazolylmethyl)-2-(nitroimino)imidazolidine weighed 1.4g.

mp. 147°-150° C.

Example 22 ##STR77##

By the procedure described in example 7 gummy substance was obtainedfrom 2.3 g of ethyl nitro(tetrahydro-2H-1,3-thiazin-2-ylidene)acetateand 1.6 g of 2-chloro-5-pyridylmethylchloride. This was triturated inethanol and insoluble material was washed with hexane, then was purifiedby chromatography on a silicagel column. The desired ethyl[3-(2-chloro-5-pyridylmethyl)tetrahydro-2H-1,3-thiazin-2-ylidene]acetateweighed 0.2 g.

mp. 180°-184° C.

Example 23 ##STR78##

5.8 g of 2-imino-3-(4-pyridylmethyl)thiazolidine was added to 20 ml ofconc. sulfuric acid at -5°˜0° C. 6 ml of fuming nitric acid was thenadded dropwise to the solution at the same temperature. After stirringfor 30 minutes at 0°˜5° C., the reaction mixture was poured onto crushedice. Twice extract with dichloromethan followed by treating in the usualway yielded 1.4 g of desired2-nitroimino-3-(4-pyridylmethyl)thiazolidine.

mp. 151°-152° C.

Example 24 ##STR79##

A mixture of 2.7 g of3-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)thiazolidine, 3.5 g ofmethyl vinylketone and 30 ml of chloroform was stirred for 2 days at 40°C. under nitrogen atmosphere. 3.5 g of methyl vinylketone was then addedto the reaction mixture and stirred again for 2 days at the sametemperature. After volatile material was removed in vacuum, the residuewas purified by chromatography on silicagel column. The desired3-(2-chloro-5-pyridylmethyl)-2-(1-nitro-4-oxopentylidene)thiazolidineweighed 0.1 g.

mp. 75°-80° C.

Example 25 ##STR80##

A mixture of 2.3 g of1-(4-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine, 0.5 g ofparoformaldehyde and 30 ml of dioxane was vigorously stirred for 2 hoursat 70°-80° C. After the reaction, the dioxane was evaporated to aboutone third of its volume under reduced pressure. The crystallized productwas filtered and dried. The yield of desiredbis-[α-nitro-1-(4-pyridylmethyl)tetrahydropyrimidin-2-ylidenemethyl]methane was 1.8 g.

mp. 222°-223° C.

Example 26 ##STR81##

To a solution of 2.4 g of1-(3-methyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidineand 30 ml of dry dichloromethane was added 1.6 g oftrichloroacetaldehyde at room temperature. After stirring for 3 hours at25°-30° C., crystallized product was filtered, washed with ether anddried. The desired1-(3-methyl-5-isoxazolylmethyl)-2-(1-nitro-2-hydroxy-3,3,3-trichloropropylidene)tetrahydropyrimidineweighed 3.1 g.

mp. 128°-130° C. (decomp.).

Example 27 ##STR82##

2.5 g of 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidinewas dissolved in 40 ml of dry dichloromethane and 10 ml of water wasadded. A solution of 1.6 g bromine in 10 ml of dichloromethane was addedto the mixture within 10 minutes at 0°-5° C. with stirring. Afterstirring for 10 minutes at 0°-5° C., crystallized product was filtered,washed with cold water and a small quantity of dichloromethane anddried. The yield of1-(2-chloro-5-pyridylmethyl)-2-(bromonitromethylene)imidazolidine was2.5 g.

mp. 110°-115° C. (decomp.).

Example 28 ##STR83##

To a mixture of 1.2 g of finely powdered1-(4-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine in 20 ml ofmethanol was added 2 drops of conc. sulfuric acid and then 1.6 g of 25%aqueous glyoxylic acid. The mixture was stirred for 3 hours at roomtemperature. After adjusting to pH 7, the precipitated product wasfiltered, washed with water, methanol and ether respectively and dried.The desired3-[1-(4-pyridylmethyl)-1H,4H,5H,6H-tetrahydropyrimidin-4-yl]-3-nitroacrylic acid weighed 1.1 g.

mp. 150°-155° C. (decomp.).

Example 29 ##STR84##

3.1 g of phenylchloroformate was added to a solution of 1.6 g of1-methylimidazole in 50 ml of dichloromethane below 0° C. After stirringfor 30 minutes at the same temperature, 2.5 g of1-(2-chloro-5-pyridylmethyl)-(2-nitromethylene)imidazolidine was addedto the mixture and the resulting mixture was stirred for 24 hours atroom temperature. The mixture was then washed with water, 1%hydrochloric acid and 1% sodium hydroxide solution respectively.Removing the dichloromethane by distillation gives glassy phenylnitro{1-(2-chloro-5-pyridylmethyl)-3-phenoxycarbonylimidazolidin-2-ylidene}acetate(3.2 g). This was then dissolved in 20 ml of dimethylformamide, 1.7 g ofsodium carbonate was added to the solution, and the mixture was stirredfor 3 days at room temperature. Water was then added and the organiclayer was extracted with dichloromethane. The extract was washed with 1%sodium hydroxide solution and water. After evaporation ofdichloromethane, the residue was purified by chromatography on asilicagel column. The desired product, phenylnitro{1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene}acetate weighed0.2 g. mp. 224°-228° C. (decomp.).

Example 30 ##STR85##

0.2 g of sodium hydride 60% in oil was added to a solution of 1.1 g of1-(3-methylisoxazol-5-ylmethyl)-2-nitroiminoimidazolidine in 15 ml ofdry dimethylformamide and the mixture was stirred until the generationof hydrogen gas ceased. 1.2 g of 2-methyl-5-nitrobenzenesulfonylchloridewas then added to the mixture. After stirring for 1 day at roomtemperature, the reaction mixture was poured into ice water, and theorganic layer was extracted with dichloromethane. The dichloromethanewas removed by distillation to give crystalline product, and this waswashed with ether. The desire1-(2-methyl-5-nitrobenzenesulfonyl)-3-(3-methylisoxazol-5-ylmethyl)-2-nitroiminoimidazolidineweighed 1.1 g.

mp. 154°-156° C.

Example 31 ##STR86##

0.2 g of sodium hydride 60% in oil was added to a solution of 1.3 g of1-(2-chloro-5-pyridylmethyl)-2-nitromethyleneimidazolidine in 15 ml ofdry dimethylformamide, and the mixture was stirred at room temperatureuntil the generation of hydrogen gas ceased. 0.9 g of4-chlorobenzenesulfenylchloride was then drop into the solution at 0° C.with stirring. After stirring for 1 hour at room temperature, thereaction mixture was poured into ice water. The precipitate crystal wasfiltered and recrystalized from ethyl acetate to give1-(2-chloro-5-pyridylmethyl)-2-{(4-chlorophenylthio)nitromethylene}imidazolidine.The yield was 1.3 g.

mp. 159°-161° C.

Example 32 ##STR87##

A solution of 0.9 g of benzenesulfonylisocyanate in 10 ml of drydichloromethane was added dropwise to a solution of 1.3 g of1-(2-chloro-5-pyridylmethyl)-2-nitromethyleneimidazolidine in 25 ml ofdry dichloromethane at room temperature. The solution was stirred for 2hours at the same temperature and then about a half volume ofdichloromethane was evaporated under reduced pressure. The product whichcrystallized was filtered and washed with ether. The desiredN-benzenesulfonyl-2-{1-(2-chloro-5-pyridylmethyl)imidazolidin-2-ylidene}-2-nitroacetamideweighed 1 g.

mp. 95°-100° C.

Example 33 ##STR88##

A mixture of 2.2 g of 2-nitroimino-1-(3-pyridylmethyl)imidazolidine, 1.6g of 2-chloro-5-chloromethylpyridine, 1.4 g of anhydrous potassiumcarbonate in 30 ml of acetonitrile was refluxed for 16 hours withstirring. The acetonitrile was then removed under reduced pressure,dichloromethane was added to the residue and was washed with water and1% sodium hydroxide solution. The residue after removing dichloromethaneunder reduced pressure was purified by chromatography on a silicagelcolumn to give1-(2-chloro-5-pyridylmethyl-2-nitroimino-3-(3-pyridylmethyl)imidazolidine.The yield was 2.1 g.

mp. 143°-144° C.

Example 34 ##STR89##

0.4 g of sodium hydride 60% in oil was added portionwise to a solutionof 2.6 g of 1-(2-chloro-5-pyridylmethyl)-2-nitroiminoimidazolidine in 20ml of dry dimethylformamide. The mixture was stirred at room temperatureuntil the evolution of hydrogen eased. A solution of 1.5 g of isopropylbromide in 5 ml of dry dimethylformamide was added dropwise to themixture at room temperature and stirred for 3 hours at room temperatureafter the addition. The reaction mixture was then poured into ice water,and the precipitated crystals filtered. This was recrystallized fromethanol to give1-(2-chloro-5-pyridylmethyl)-3-isopropyl-2-nitroiminoimidazolidine. Theyield was 1.5 g.

mp. 138°-142° C.

Example 35 ##STR90##

A mixture of 2.7 g of3-(2-chloro-5-pyridylmethyl)-2-nitromethylenethiazolidine and 8 ml ofbutyric anhydride was stirred for 8 hours at 60° C. under nitrogenatmosphere. The volatile material was then removed by distillation at 1mmHg, keeping the bath temperature below 60° C. The residue wasdissolved in dichloromethane and washed with 1% sodium hydroxidesolution. The dichloromethane layer was then purified by chromatographyon a silicagel column to give viscous oily1-{3-(2-chloro-5-pyridylmethyl)thiazolidine-2-ylidene}-1-nitro-2-pentanone.The yield was 0.15 g.

n_(D) ²⁰ 1.6342.

In accordance with the same method as in the above examples, thecompounds of the formula (I) are shown in the following tables.

In the tables, "--" for R³ and R⁴ means n is 0 and in such case, thecorresponding ring-structure is 5-membered heterocyclic ring.

The case where X is a sulfur atom and the formula (I) represents thefollowing formula: (table 1) ##STR91##

                  TABLE 1                                                         ______________________________________                                                               Bonding posi-                                          Compound               tions of the                                           No.     m     R        pyridine ring                                                                          Q.sub.l                                       ______________________________________                                        36      2     H        5-       2-F                                           37      3     H        5-       2-F                                           38      2     CH.sub.3 5-       2-Cl                                          39      2     H        5-       2-Br                                          40      2     H        5-       2,3-Cl.sub.2                                  41      2     H        5-       2,3,4,6-F.sub.4                               42      2     H        4-       2-Cl                                          43      3     H        5-       2-Br                                          44      2     H        5-       2-F, 3-Cl                                     45      2     H        2-       3-Cl                                          46      3     H        2-       5-Cl                                          47      2     H        2-       3,5-Cl.sub.2                                  48      3     H        2-       5-F                                           49      2     H        2-       6-Br                                          50      3     H        3-       2-Cl                                          51      3     H        3-       5-Cl                                          52      2     H        3-       5-Br                                          53      2     H        3-       5-F                                           54      2     CH.sub.3 5-       2-F                                           55      3     H        5-       2,4-Cl.sub.2                                  56      2     H        5-       2,4-Br.sub.2                                  57      2     H        4-       2,6-F.sub.2                                   58      3     H        4-       2-F                                           59      2     H        4-       2,6-Br.sub.2                                  60      2     H        5-       2-F, 3-Br                                     61      2     H        5-       2-Cl, 3-F                                     62      2     C.sub.2 H.sub.5                                                                        5-       2-Cl.sub.3                                    63      2     H        4-       --                                            64      3     H        4-       --                                            65      2     H        5-       2-CH.sub.3                                    66      3     H        5-       2-CH.sub.3                                    67      2     H        5-       2-C.sub.2 H.sub.5                             68      2     H        5-       2-CH.sub.2 CHCH.sub.2                         69      2     H        5-       2-CH.sub.2 CCH                                70      3     H        5-       2-OCH.sub.3                                   71      2     H        5-       2-SCH.sub.3                                   72      2     H        5-                                                                                      ##STR92##                                    73      2     H        5-       2-Cl, 3-CH.sub.3                              74      2     CH.sub.3 3-       --                                            75      2     H        5-       2-CF.sub.3                                    76      3     H        5-       2-CF.sub.3                                    77      2     H        5-       2-NO.sub.2                                    78      3     H        5-       2-NO.sub.2                                    79      2     H        5-       2-CN                                          80      3     H        5-       2-CN                                          81      2     H        5-                                                                                      ##STR93##                                    82      2     H        5-                                                                                      ##STR94##                                    83      2     H        5-                                                                                      ##STR95##                                    84      3     H        5-                                                                                      ##STR96##                                    85      2     H        5-       2-CCl.sub.3                                   86      3     H        5-       2-C.sub.2 H.sub.4 OC.sub.2 H.sub.5            87      2     H        5-       2-CH.sub.2 OCH.sub.3                          88      2     H        5-       2-OCHF.sub.2                                  89      2     H        5-       2-OCF.sub.3                                   90      2     H        5-       2-OCH.sub.2 CF.sub.3                          91      3     H        5-       2-SCClF.sub.2                                 92      2     H        5-       2-SCF.sub.3                                   93      2     H        5-       2-CHF.sub.2                                   94      2     H        5-                                                                                      ##STR97##                                    95      2     H        5-                                                                                      ##STR98##                                    96      2     H        5-       2-CHCCl.sub.2                                 ______________________________________                                    

Besides table 1, the case where X is a sulfur atom: (table 2)

                                      TABLE 2                                     __________________________________________________________________________     ##STR99##                                                                    Comp.                                                                         No. Z              R R.sup.1                                                                         R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         n Y                                         __________________________________________________________________________     97                                                                                ##STR100##    H H H  --                                                                              --                                                                              H H 0 N                                          98                                                                                ##STR101##    H H H  --                                                                              --                                                                              H H 0 N                                          99                                                                                ##STR102##    H H H  --                                                                              --                                                                              H H 0 N                                         100                                                                                ##STR103##    H H H  H H H H 1 N                                         101                                                                                ##STR104##    H H H  --                                                                              --                                                                              H H 0 N                                         102                                                                                ##STR105##    H H H  --                                                                              --                                                                              H H 0 N                                         103                                                                                ##STR106##    H H H  H H H H 1 N                                         104                                                                                ##STR107##    H H H  --                                                                              --                                                                              H H 0 N                                         105                                                                                ##STR108##    H H H  --                                                                              --                                                                              H H 0 N              mp. 143-145°                                                          C.                          106                                                                                ##STR109##    H H H  --                                                                              --                                                                              H H 0 N                                         107                                                                                ##STR110##    H H H  H H H H 1 N                                         108                                                                                ##STR111##    H H H  --                                                                              --                                                                              H H 0 N                                         109                                                                                ##STR112##    H H H  --                                                                              --                                                                              H H 0 N                                         110                                                                                ##STR113##    H H H  H H H H 1 N                                         111                                                                                ##STR114##    H H H  --                                                                              --                                                                              H H 0 N                                         112                                                                                ##STR115##    H H H  --                                                                              --                                                                              H H 0 CH                                        113                                                                                ##STR116##    H H H  --                                                                              --                                                                              H H 0 CH                                        114                                                                                ##STR117##    H H H  H H H H 1 CH                                        115                                                                                ##STR118##    H H H  --                                                                              --                                                                              H H 0 CH                                        116                                                                                ##STR119##    H H H  --                                                                              --                                                                              H H 0 N                                         117                                                                                ##STR120##    H H H  --                                                                              --                                                                              H H 0 N                                         118                                                                                ##STR121##    H H H  --                                                                              --                                                                              H H 0 N                                         119                                                                                ##STR122##    H H H  --                                                                              --                                                                              H H 0 N                                         120                                                                                ##STR123##    H H H  H H H H 1 CCH.sub.3                                 121                                                                                ##STR124##    H H H  --                                                                              --                                                                              H H 0 CCH.sub.2 F                               122                                                                                ##STR125##    H H H  --                                                                              --                                                                              H H 0 CCF.sub.3                                 123                                                                                ##STR126##    H H H  --                                                                              --                                                                              H H 0 CCH.sub.2 OCH.sub.3                       124                                                                                ##STR127##    H H H  --                                                                              --                                                                              H H 0 CCH.sub.2 SC.sub.2 H.sub.5                125                                                                                ##STR128##    H H H  H H H H 1 CCH.sub.2 N(CH.sub.3).sub.2               126                                                                                ##STR129##    H H H  H H H H 1 CCH.sub.2 CHCH.sub.2                      127                                                                                ##STR130##    H H H  --                                                                              --                                                                              H H 0 C(CH.sub.2).sub.2 CN                      128                                                                                ##STR131##    H H H  --                                                                              --                                                                              H H 0 C(CH.sub.2).sub.2 COOCH.sub.3             129                                                                                ##STR132##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR133##                               130                                                                                ##STR134##    H H H  H H H H 1                                                                                ##STR135##                               131                                                                                ##STR136##    H H H  --                                                                              --                                                                              H H 0 CCOCH.sub.3   n.sub.D.sup.25 1.6358       132                                                                                ##STR137##    H H H  H H H H 1 CCOCH.sub.2 OCH.sub.3                     133                                                                                ##STR138##    H H H  --                                                                              --                                                                              H H 0 CCOCCl.sub.3                              134                                                                                ##STR139##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR140##                               135                                                                                ##STR141##    H H H  H H H H 1                                                                                ##STR142##                               136                                                                                ##STR143##    H H H  H H H H 1 CCOOCH.sub.3                              137                                                                                ##STR144##    H H H  H H H H 1 CCOOC.sub.2 H.sub.5                       138                                                                                ##STR145##    H H H  --                                                                              --                                                                              H H 0 CCOOC.sub.2 H.sub.5                       139                                                                                ##STR146##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR147##                               140                                                                                ##STR148##    H H H  --                                                                              --                                                                              H H 0 CS(CH.sub.2).sub.3 CH.sub.3               141                                                                                ##STR149##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR150##                               142                                                                                ##STR151##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR152##                               143                                                                                ##STR153##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR154##                               144                                                                                ##STR155##    H H CH.sub.3                                                                         --                                                                              --                                                                              H H 0 N                                         145                                                                                ##STR156##    H H H  --                                                                              --                                                                              H H 0                                                                                ##STR157##                               146                                                                                ##STR158##    H H H  H H H H 1 CCOOC.sub.2 H.sub.5                                                                         n.sub.D.sup.24 1.5978       147                                                                                ##STR159##    H H H  --                                                                              --                                                                              H H 0 CCOCH.sub.3                               148                                                                                ##STR160##    H H H  --                                                                              --                                                                              H H 0 CCOOCH.sub.3                              149                                                                                ##STR161##    H H H  --                                                                              --                                                                              H H 0 CCOOCH.sub.2 CF.sub.3                     150                                                                                ##STR162##    H H H  --                                                                              --                                                                              H H 0 CH                                        151                                                                                ##STR163##    H H H  H H H H 1 CH                                        152                                                                                ##STR164##    H H H  H H H H 1 CH                                        153                                                                                ##STR165##    H H H  --                                                                              --                                                                              H H 0 CH                                        154                                                                                ##STR166##    H H H  H H H H 1 CH                                        155                                                                                ##STR167##    H H H  H H H H 1 CH                                        156                                                                                ##STR168##    H H H  H H H H 1 CH                                        157                                                                                ##STR169##    H H H  --                                                                              --                                                                              H H 0 CH                                        158                                                                                ##STR170##    H H H  --                                                                              --                                                                              H H 0 CH                                        159                                                                                ##STR171##    H H H  --                                                                              --                                                                              H H 0 CH                                        160                                                                                ##STR172##    H H H  H H H H 1 CH                                        __________________________________________________________________________

The case where X is CH--R⁸ : (table 3)

                                      TABLE 3                                     __________________________________________________________________________     ##STR173##                                                                   Comp.                                                                         No. Z              R  R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         n R.sup.8  Y                                __________________________________________________________________________    161                                                                                ##STR174##    CH.sub.3                                                                         H H H --                                                                              --                                                                              H 0 H        CH                               162                                                                                ##STR175##    H  H H H H H H 1 H        CH                               163                                                                                ##STR176##    H  H H --                                                                              --                                                                              H H 0 H        CH                               164                                                                                ##STR177##    H  H H --                                                                              --                                                                              H H 0 H        CH                               165                                                                                ##STR178##    H  H H --                                                                              --                                                                              H H 0 H        CH                               166                                                                                ##STR179##    H  H H --                                                                              --                                                                              H H 0 H        CH                               167                                                                                ##STR180##    H  H H --                                                                              --                                                                              H H 0 H        CH                               168                                                                                ##STR181##    H  H H --                                                                              --                                                                              H H 0 H        CH                               169                                                                                ##STR182##    H  H H --                                                                              --                                                                              H H 0 H        N                                170                                                                                ##STR183##    H  H H H H H H 1 H        N           n.sub.D.sup.20                                                                1.5995               171                                                                                ##STR184##    H  H H --                                                                              --                                                                              H H 0 H        N                                172                                                                                ##STR185##    H  H H --                                                                              --                                                                              H H 0 H        N                                173                                                                                ##STR186##    CH.sub.3                                                                         H H --                                                                              --                                                                              H H 0 H        CH                               174                                                                                ##STR187##    H  H H --                                                                              --                                                                              H H 0 H        CH                               175                                                                                ##STR188##    H  H H H H H H 1 H        CH                               176                                                                                ##STR189##    H  H H --                                                                              --                                                                              H H 0 H        CH                               177                                                                                ##STR190##    H  H H --                                                                              --                                                                              H H 0 H        CH                               178                                                                                ##STR191##    H  H H H H H H 1 H        CH                               179                                                                                ##STR192##    H  H H --                                                                              --                                                                              H H 0 H        CH                               180                                                                                ##STR193##    H  H H --                                                                              --                                                                              H H 0 H        N                                181                                                                                ##STR194##    H  H H H H H H 1 H        N                                182                                                                                ##STR195##    H  H H --                                                                              --                                                                              H H 0 H        N                                183                                                                                ##STR196##    H  H H --                                                                              --                                                                              H H 0                                                                                ##STR197##                                                                            N                                184                                                                                ##STR198##    H  H H --                                                                              --                                                                              H H 0 H        N                                185                                                                                ##STR199##    H  H H H H H H 0 H        CH                               186                                                                                ##STR200##    H  H H --                                                                              --                                                                              H H 0 H        CH                               187                                                                                ##STR201##    CH.sub.3                                                                         H H --                                                                              --                                                                              H H 0                                                                                ##STR202##                                                                            CH                               188                                                                                ##STR203##    H  H H --                                                                              --                                                                              H H 0 H        CH                               189                                                                                ##STR204##    H  H H --                                                                              --                                                                              H H 0 H        N                                190                                                                                ##STR205##    H  H H --                                                                              --                                                                              H H 0 H        N                                191                                                                                ##STR206##    H  H H --                                                                              --                                                                              H H 0 H        N                                192                                                                                ##STR207##    H  H H --                                                                              --                                                                              H H 0 H        N                                193                                                                                ##STR208##    H  H H H H H H 1 CH.sub.3 CH                               194                                                                                ##STR209##    H  H H --                                                                              --                                                                              H H 0 H        CCOOC.sub.2 H.sub.5              195                                                                                ##STR210##    H  H H --                                                                              --                                                                              H H 0 H                                                                                       ##STR211##                      196                                                                                ##STR212##    H  H H --                                                                              --                                                                              H H 0 H        CBr                              197                                                                                ##STR213##    H  H H H H H H 1 H                                                                                       ##STR214##                      198                                                                                ##STR215##    H  H H --                                                                              --                                                                              H H 0 CH.sub.3 N                                __________________________________________________________________________

The case where X is an oxygen atom: (table 4)

                                      TABLE 4                                     __________________________________________________________________________     ##STR216##                                                                   Comp.                                                                         No. Z          R R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          R.sup.6                                                                         n Y                                             __________________________________________________________________________    199                                                                                ##STR217##                                                                              H H H --                                                                              --                                                                              H  H 0 CH         mp. 137-140° C.             200                                                                                ##STR218##                                                                              H H H H H H  H 1 CH                                            201                                                                                ##STR219##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            202                                                                                ##STR220##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            203                                                                                ##STR221##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            204                                                                                ##STR222##                                                                              H H H --                                                                              --                                                                              H  H 0 N                                             205                                                                                ##STR223##                                                                              H H H --                                                                              --                                                                              H  H 0 N                                             206                                                                                ##STR224##                                                                              H H H --                                                                              --                                                                              H  H 0 N                                             207                                                                                ##STR225##                                                                              H H H --                                                                              --                                                                              H  H 0 N                                             208                                                                                ##STR226##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            209                                                                                ##STR227##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            210                                                                                ##STR228##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            211                                                                                ##STR229##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            212                                                                                ##STR230##                                                                              H H H H H H  H 1 CH                                            213                                                                                ##STR231##                                                                              H H H H H H  H 1 CH                                            214                                                                                ##STR232##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            215                                                                                ##STR233##                                                                              H H H H H H  H 1 CH                                            216                                                                                ##STR234##                                                                              H H H --                                                                              --                                                                              H  H 0 N                                             217                                                                                ##STR235##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            218                                                                                ##STR236##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            219                                                                                ##STR237##                                                                              H H H --                                                                              --                                                                              H  H 0 CH                                            220                                                                                ##STR238##                                                                              H H H --                                                                              --                                                                              H  H 0 CCH.sub.3                                     221                                                                                ##STR239##                                                                              H H H --                                                                              --                                                                              CH.sub.3                                                                         H 0 CH                                            222                                                                                ##STR240##                                                                              H H H --                                                                              --                                                                              H  H 0                                                                                ##STR241##                                   223                                                                                ##STR242##                                                                              H H H --                                                                              --                                                                              H  H 0                                                                                ##STR243##                                   224                                                                                ##STR244##                                                                              H H H --                                                                              --                                                                              H  H 0 CCO(CH.sub.2).sub.2 CH.sub.3                  __________________________________________________________________________

The case where the formula (I) represents the following formula: (table5) ##STR245##

                                      TABLE 5                                     __________________________________________________________________________                   Bonding posi-                                                  Compound       tion on the                                                    No.   m r      pyridine ring                                                                        Q.sub.l                                                 __________________________________________________________________________    225   2 H      3-     --       m.p. 90-94° C. (dec.)                   226   3 H      3-     --                                                      227   2 CH.sub.3                                                                             3-     --                                                      228   2 C.sub.2 H.sub.5                                                                      3-     --                                                      229   2 CH(CH.sub.3).sub.2                                                                   3-     --                                                      230   2 H      4-     --       m.p. 154-157° C.                        231   3 H      4-     --       m.p. 163-165° C.                        232   2 H      2-     5-Cl                                                    233   3 H      5-     2-F                                                     234   2 CH.sub.3                                                                             5-     2-Cl                                                    235   2 H      5-     2-Br                                                    236   2 H      5-     2-CH.sub.3                                                                             m.p. 157-160° C.                        237   3 H      5-     2-CH.sub. 3                                                                            m.p. 155.5-158.5° C.                    238   2 H      5-     2-CH.sub.2 H.sub.5                                      239   2 H      5-     2-OCH.sub.3                                             240   2 H      5-     2-OC.sub.2 H.sub.5                                      241   2 H      5-     2-SCH.sub.3                                             242   2 H      5-     2-NO.sub.2                                              243   2 H      5-     2-CN                                                    244   2 H      5-     2-NH.sub.2                                              245   3 H      5-                                                                                    ##STR246##                                             246   2 H      5-     2-N(CH.sub.3).sub.2                                     247   2 H      5-                                                                                    ##STR247##                                             248   2 H      5-                                                                                    ##STR248##                                             249   2 H      5-                                                                                    ##STR249##                                             250   2 H      5-                                                                                    ##STR250##                                             251   2 H      5-     2-CHF.sub.2                                             252   2 H      5-     2-CF.sub.3                                                                             mp. 134-146° C.                         253   3 H      5-     2-CF.sub.3                                              254   2 H      5-     2-CCl.sub.3                                             255   2 H      5-     2-CF.sub.2 Cl                                           256   2 H      5-     2-CH.sub.2 CH.sub.2 F                                   257   2 H      5-     2-CH.sub.2 CH.sub.2 Cl                                  258   2 H      5-     2-CH.sub.2 CF.sub.3                                     259   3 H      5-     2-OCHF.sub.2                                            260   2 H      5-     2-OCF.sub.3                                             261   3 H      5-     2-OCH.sub.2 CF.sub.3                                    262   2 H      5-     2-SCF.sub.3                                             263   2 H      5-     2-SCF.sub.2 Cl                                          264   2 H      5-     3-Br     m.p. 198-201° C.                        265   2 H      5-     5-CF.sub.3                                              266   2 H      5-     2-CH.sub.2 CCH                                          267   2 H      5-     2-CH.sub.2 CHCH.sub.2                                   268   2 H      5-     2-CHC(Cl).sub.2                                         269   2 H      5-     2,4-Cl.sub.2                                            270   2 H      5-     2-Cl, 3-CH.sub.3                                        271   2 H      4-     2,3,5,6-F.sub.4                                         272   2 H      5-     2-CHO                                                   273   2 H      5-     2-CF.sub.2 Br                                           __________________________________________________________________________

The case where Z is optionally substituted-pyridyl and X is N--R⁷ :(table 6)

The formula (I) has the following formula; ##STR251##

In the table 5, "--" for Q_(l) means no substituent and "--" for both R²and R⁵ mean that R² forms a single bond, together with R⁵.

    TABLE 6      ##STR252##         Bonding positions            Comp. No. Q.sub.l of the pyridine ring     R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 n R.sup.7 Y       274 -- 4-position H H CH.sub.3 -- -- H H 0 H CH mp.     184-187° C. 275 -- 3-position CH.sub.3 H CH.sub.3 -- -- H H 0 H     CH 276 -- 3-position H CH.sub.3 CH.sub.3 -- -- H H 0 H CH mp.       177-180° C. 277 -- 4-position H H H CH.sub.3 CH.sub.3 H H 1 H     CH mp.              190-191° C. 278 -- 4-position H H H OH H H H     1 H CH mp.              209-212° C. 279 2-F 5-position H H     CH.sub.3 -- -- H H 0 H CH 280 2-Cl 5-position H H H H CH.sub.3 H H 1 H     CH 281 2-Cl 5-position H H C.sub.2 H.sub.5 -- -- H H 0 H CH 282 2-Cl     5-position H H CH.sub.3 -- -- CH.sub.3 H 0 H CH 283 2-Br 5-position H H     CH.sub.3 -- -- H H 0 H CH 284 2-CF.sub.3 5-position H H CH.sub.3 -- -- H     H 0 H CH 285 2-CH.sub.3 5-position H H CH.sub.3 -- -- H H 0 H CH 286     2-CF.sub.3 5-position H H CH.sub.3 -- -- H H 0 H CH 287 2-NO.sub.2,     5-position H H CH.sub.3 -- -- H H 0 H CH  3-OCH.sub.3 288 -- 3-position     H H H -- -- H H 0 CH.sub.3 CH mp.              107-110° C. 289     2-F 5-position H H H -- -- H H 0 CH(CH.sub.3).sub.2 CH 290 2-Cl 5-positio     n H H H -- -- H H 0 CH.sub.3 CH mp.              128-130° C. 291     2-Cl 5-position H H H H H H H 1 CH.sub.3 CH 292 2-Cl 5-position H H H --     -- H H 0 OH CH 293 2-Cl 5-position H H H -- -- H H 0 OC.sub.2 H.sub.5 CH      294 2-Cl 5-position H H H -- -- H H 0     ##STR253##      CH  295 2-Cl 5-position H H H -- -- H H 0 CH.sub.2 OC.sub.2 H.sub.5 CH     296 2-Cl 5-position H H H -- -- H H 0 CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9     CH 297 2-Cl 5-position H H H -- -- H H 0 CH.sub.2 CH.sub.2 SC.sub.2     H.sub.5 CH 298 2-Cl 5-position H H H -- -- H H 0 CH.sub.2 CHCH.sub.2 CH     299 2-Cl 5-position H H H -- -- H H 0 CH.sub.2 CH.sub.2 CN CH  300 --     3-position H H H -- -- H H 0      ##STR254##      CH mp.175-178° C.      301 -- 4-position H H H -- -- H H 0     ##STR255##      CH mp.176-180° C.      302 2-F 5-position H H H H H H H 1     ##STR256##      CH      303 2-Cl 5-position H H H -- -- H H 0     ##STR257##      CH mp.152-153° C.  304 2-Cl 5-position H H H -- -- H H 0      ##STR258##      CH mp.158-160° C.  305 2-Cl 5-position H H H -- -- H H 0      ##STR259##      CH      306 2-CH.sub.3 5-position H H H -- -- H H 0     ##STR260##      CH      307 2-Cl 5-position H H H -- -- H H 0     ##STR261##      CH n.sub.D.sup.20 1.6495  308 2-Cl 5-position H H H -- -- H H 0      ##STR262##      CH mp.154-156° C.      309 2-F 5-position H H H -- -- H H 0     ##STR263##      CH      310 2-Cl 5-position H H H -- -- H H 0     ##STR264##      CH n.sub.D.sup.20 1.6480  311 2-Br 5-position H H H -- -- H H 0      ##STR265##      CH      312 2-Cl 5-position H H H -- -- H H 0     ##STR266##      CH      313 2-Cl 5-position H H H -- -- H H 0     ##STR267##      CH  314 -- 3-position H H H --  -- H H 0 H CCl 315 2-Cl 5-position H H     H -- -- H H 0 H CF 316 2-Cl 5-position H H CH.sub.3 -- -- H H 0 H CBr     317 -- 4-position H H H H H H H 1 H CCH.sub.3 318 2-Cl 5-position H H H     -- -- H H 0 H CCH.sub.3 319 2-Cl 5-position H H H -- -- H H 0 H CCH.sub.2      F 320 2-Cl 5-position H H H -- -- H H 0 H CCF.sub.3 321 -- 3-position H     H H -- -- H H 0 H CCH.sub.2 OH  322 2-F 5-position H H H H H H H 1 H      ##STR268##      323 2-Cl 5-position H H H -- -- H H 0 H     ##STR269##      mp.135-140° C.      324 2-Cl 5-position H H H -- -- H H 0 H     ##STR270##      mp.155-158° C.  325 -- 3-position H H H H H H H 1 H COH 326 2-Cl     5-position H H H -- -- H H 0 H COCH.sub.3  327 2-Cl 5-position H H H --     -- H H 0 H      ##STR271##       328 -- 4-position H H H -- -- H H 0 H CSC.sub.3 H.sub.7      329 2-CH.sub.3 5-position H H H -- -- H H 0 H      ##STR272##      330 -- 3-position H H H -- -- H H 0 H     ##STR273##      331 2-Cl 5-position H H H -- -- H H 0 H     ##STR274##      332 2-CF.sub. 3 5-position H H H -- -- H H 0 H     ##STR275##       333 2-Cl 5-position H H H -- -- H H 0 H CCOCH.sub.3 334 2-F 5-position     H H H -- -- H H 0 H CCOCCl.sub.3 335 2-NO.sub.2 5-position H H H -- -- H     H 0 H CCOCHCH.sub.2 336 2-Cl 5-position H H H -- -- H H 0 H CCOC.sub.3     H.sub.7 mp.              102-105° C.  337 2-Cl 5-position H H H     -- -- H H 0 H      ##STR276##      mp.213-215° C.      338 -- 3-position H H H H H H H 1 H     ##STR277##       339 -- 4-position CH.sub.3 H H -- -- H H 0 H CCOOCH.sub.3 340 2-Cl     5-position H H H -- -- H H 0 H CCOOC.sub.2 H.sub.5 mp.     169-171° C. 341 2-CN 5-position H H H -- -- H H 0 H CCOOC.sub.4     H.sub.9      342 2-F 5-position H H H -- -- H H 0 H     ##STR278##      343 2-Cl 5-position H H H -- -- H H 0 H     ##STR279##       344 2-Cl 5-position H H H -- -- H H 0 H CCOSC.sub.4 H.sub.9  345 2-Cl     5-position H H H -- -- H H 0 H      ##STR280##      mp.89-94° C.(decomp.)  346 2-CF.sub.3 5-position H H H -- -- H H     0 H      ##STR281##      347 2,3-Cl.sub.2 5-position H H H -- -- H H 0 H     ##STR282##      348 2-CHF.sub.2 5-position H H H -- -- H H 0 H     ##STR283##       349 -- 3-position H H H -- -- H H 0 CH.sub.3 CCOCH.sub.3 350 2-Cl     5-position H H H -- -- H H 0 CH.sub.3 CCOC.sub.3 H.sub.7 mp.      100-105° C. 351 2-Cl 5-position H H H -- -- H H 0 COCH.sub.3     CCOCH.sub.3 352 2-CH.sub.3 5-position H H H -- -- H H 0 Cl CCl 353 --     3-position H H H H H H H 1 COOC.sub.2 H.sub.5 CCOOC.sub.2 H.sub.5  354     2-Cl 5-position H H H -- -- H H 0      ##STR284##      ##STR285##      glass      355 2-CF.sub.3 5-position H H H -- -- H H 0     ##STR286##      ##STR287##      356 -- 4-position H H H -- -- H H 0     ##STR288##      ##STR289##      357 2-Cl 5-position H H H -- -- H H 0     ##STR290##      ##STR291##       358 -- 3-position H H H CH.sub.3 H H H 1 H N 359 2-Cl 5-position H H     CH.sub.3 -- -- H H 0 H N 360 2-Cl 5-position H CH.sub.3 CH.sub.3 -- -- H     H 0 H N 361 2-Cl 5-position H H H -- -- H H 0 CH.sub.3 N 362 2-SCN     5-postion H H H -- -- H H 0 CH(CH.sub.3).sub.2 N 363 2-F 5-position H H     H -- -- H H 0 CH.sub.2 CH.sub.2 Cl N 364 2-Cl 5-position H H H -- -- H H     0 CH.sub.2 CHCH.sub.2 N n.sub.D.sup.30 1.5854 365 2-Cl 5-position H H H     -- -- H H 0 CH.sub.2 CClCCl.sub.2 N 366 2-Cl 5-position H H H -- -- H H     0 CH.sub.2 CH.sub.2 CN N 367 2-F 5-position H H H -- -- H H 0 CH.sub.2     CCH N 368 2-CF.sub.3 5-position H H H -- -- H H 0 CH.sub.2 CH.sub.2     N(C.sub.2 H.sub.5).sub.2 N 369 2-Cl 5-position H H H H H H H 1 CH.sub.2     OCH.sub.3 N 370 -- 3-position H H H -- -- H H 0 CH.sub.2 CH.sub.2     SC.sub.2 H.sub.5 N 371 2-CH.sub.2 F 5-position H H H -- -- H H 0     CH.sub.2 SC.sub.4 H.sub.9 N 372 2-Cl 5-position H H H -- -- H H 0     CH.sub.2 CN N 373 2-Cl 5-position H H H -- -- H H 0 CH.sub.2      Si(CH.sub.3).sub.3 N 374 5-CF.sub.3 2-position H H H -- -- H H 0     CH.sub.2 Si(CH.sub.3).sub.3 N  375 2-Cl 5-position H H H H H H H 1      ##STR292##      N      376 2-NO.sub.2 5-position H H H -- -- H H 0     ##STR293##      N      377 -- 3-position H H H -- -- H H 0     ##STR294##      N      378 2-Cl 5-position H H H -- -- H H 0     ##STR295##      N      379 5-OCF.sub.3 2-position H H H -- -- H H 0     ##STR296##      N      380 2-Cl 5-position H H H -- -- H H 0     ##STR297##      N mp.126-128° C.  381 2-Cl 5-position H H H -- --  H H 0      ##STR298##      N mp.146-148° C.      382 2-Cl 5-position H H H -- -- H H 0     ##STR299##      N mp.128-131° C.      383 -- 3-position H H H -- -- H H 0     ##STR300##      N      384 2-CH.sub.3 5-position H H H H H H H 1     ##STR301##      N      385 2-Cl 5-position H H H H H H H 1     ##STR302##      N      386 2-Cl 5-position H H H H H H H 1     ##STR303##      N       387 2-F 5-position H H H -- -- H H 0     ##STR304##      N      388 2-Cl 5-position H H H -- -- H H 0     ##STR305##      N      389 2-Cl 5-position H H H -- -- H H 0     ##STR306##      N      390 2-CH.sub.3 5-position H H H -- -- H H 0     ##STR307##      N  391 2-F 5-position H H H -- -- H H 0 CH.sub.2 COCH.sub.3 N  392 2-Cl     5-position H H H -- -- H H 0      ##STR308##      N      393 2-Cl 5-position H H H -- -- H H 0     ##STR309##      N  394 -- 3-position CH.sub.3 H H -- -- H H 0 COCH.sub.3 N 395 2-Cl     5-position H H H -- -- H H 0 CHO N 396 2-Cl 5-position H H H -- -- H H 0     COCH.sub.3 N mp.              144.5-146° C. 397 2-Cl 5-position H     H H H H H H 1 COCH.sub.3 N 398 2-F 5-position H H H -- -- H H 0 COCCl.sub     .3 N 399 2-Cl, 5-position H H H -- -- H H 0 COC.sub.3 H.sub.7 N  4-F 400     2-C.sub.2 H.sub.5 5-position H H H -- -- H H 0 COCH.sub.3 N 401 2-Cl     5-position H H H -- -- H H 0 COC(CH.sub.3).sub.3 N  402 2-CH.sub.3     5-position H H H -- -- H H 0      ##STR310##      N  403 2,3-F.sub.2 5-position H H H -- -- H H 0 COCH.sub.2 OCH.sub.3 N     404 2-Br 5-position H H H -- -- H H 0 COCHCH.sub.2 N      405 2-Cl 5-position H H H -- -- H H 0      ##STR311##      N      406 -- 3-position H H H -- -- H H 0     ##STR312##      N      407 -- 4-position H H H H H H H 1     ##STR313##      N      408 2-Cl 5-position H H H -- -- H H 0     ##STR314##      N mp.146-150° C.      409 2-F 5-position H H H -- -- H H 0     ##STR315##      N mp.149-152° C.      410 2-Cl 5-position H H H -- -- H H 0     ##STR316##      N      411 2-Cl 5-position H H H -- -- H H 0     ##STR317##      N      412 -- 3-position H H H -- -- H H 0     ##STR318##      N      413 2-CHCCl.sub.5 5-position H H H -- -- H H 0     ##STR319##      N      414 2-CF.sub.3 5-position H H H -- -- H H 0     ##STR320##      N      415 2-CH.sub.3 5-position H H H -- -- H H 0     ##STR321##      N      416 2-Cl 5-position H H H -- -- H H 0     ##STR322##      N      417 2-Cl 5-position H H H -- -- H H 0     ##STR323##      N      418 2-Cl 5-position H H H -- -- H H 0     ##STR324##      N      419 -- 3-position H H H H H H H 1     ##STR325##      N      420 2-F 5-position H H H -- -- H H 0     ##STR326##      N      421 2-CH.sub.3 5-position H H H -- -- H H 0     ##STR327##      N      422 2-Cl 5-position H H H -- -- H H 0     ##STR328##      N      423 2,6-Cl.sub.2 4-position H H H -- -- H H 0     ##STR329##      N      424 2-Cl 5-position H H H -- -- H H 0     ##STR330##      N mp.118-122° C.      425 2-Cl 5-position H H H -- -- H H 0     ##STR331##      N  426 -- 3-position H H H H CH.sub.3 H H 1 COOCH.sub.3 N 427 2-F     5-position H H H -- -- H H 0 COOC.sub.2 H.sub.5 N 428 2-Cl 5-position H     H H -- -- H H 0 COOC.sub.2 H.sub.5 N mp.              125-126° C.     429 2-CH.sub.3 5-position H H H -- -- H H 0 COOC.sub.4 H.sub.9 N 430     2-Cl 5-position H H H -- -- H H 0 COOCH.sub.2 CF.sub.3 N  431 2-Cl     5-position H H H -- -- H H 0      ##STR332##      N mp.135-140° C.  432 2-Cl 5-position CH.sub.3 H H -- -- H H 0      ##STR333##      N      433 2-Cl 5-position H H H -- -- H H 0     ##STR334##      N      434 2-CHF.sub.2 5-position H H H -- -- H H 0     ##STR335##      N  435 2-Cl 5-position H H H -- -- H H 0 COSC.sub.2 H.sub.5 N  436 2-Cl     5-position H H H -- -- H H 0      ##STR336##      N      437 2,3-F.sub.2 5-position H H H -- -- H H 0     ##STR337##      N      438 2-Cl 5-position H H H -- -- H H 0     ##STR338##      N mp.191-192° C.      439 2-Cl 5-position H H H -- -- H H 0     ##STR339##      N      440 2-Cl 5-position H H H -- -- H H 0     ##STR340##      N      441 2-COOCH.sub.3 6-position H H H -- -- H H 0     ##STR341##      N      442 2-Cl 5-position H H H -- -- H H 0     ##STR342##      N      443 2-Cl 5-position H H H -- -- H H 0     ##STR343##      N  444 2-Cl 5-position H H H -- -- H H 0 CON(CH.sub.3).sub.2 N mp.             186-188° C.  445 2-Cl 5-position H H H -- -- H H 0      ##STR344##      N mp.120-123° C.      446 2-F 5-position H H H -- -- H H 0     ##STR345##      N      447 2-Cl,6-F 5-position H H H -- -- H H 0     ##STR346##      N      448 2-CN 5-position H H H -- -- H H 0     ##STR347##      N      449 -- 4-position H H H H H H H 1     ##STR348##      N      450 2-Cl 5-position H H H -- -- H H 0     ##STR349##      N      451 2-Cl 5-position H H H -- -- H H 0     ##STR350##      N      452 -- 3-position H H H -- -- H H 0     ##STR351##      N n.sub.D.sup.24 1.5760      453 2-Cl 5-position H H H -- -- H H 0     ##STR352##      N n.sub.D.sup.20 1.5615      454 2-Cl 5-position H H H -- -- H H 0     ##STR353##      N      455 2-Cl 5-position H H H -- -- H H 0     ##STR354##      N      456 2-Cl 5-position H H -- H H -- H 1 H CH

In addition to table 5, there follow: the case (table 7) where theformula (I) represents the following formula; ##STR355## the case (table8) where the formula (I) represents the following formula; ##STR356##

the case (table 9) where the formula (I) represents the followingformula; ##STR357## the case (table 10) where the formula (I) representsthe following formula; ##STR358##

                                      TABLE 7                                     __________________________________________________________________________    Compound Bonding potition                                                     No.   Het                                                                              of the heterocycle                                                                     Q.sub.l  R   m                                              __________________________________________________________________________    457   O  2        --       H   2                                              458   O  2        --       H   3 mp. 194˜196° C.                 459   O  3        --       H   3                                              460   S  2        --       H   2                                              461   S  2        --       H   3 mp. 189˜190° C.                 462   S  3        --       H   3 mp. 196˜198° C.                 463   S  3        --       CH.sub.3                                                                          2                                              464   N  2        1-H      H   2 mp. 201˜205° C.                 465   N  2        1-H      H   3 mp. 183˜185° C.                 466   N  3        1-H      H   3                                              467   N  2        1-CH.sub.3                                                                             H   2                                              468   N  2        1-CH.sub.3                                                                             H   3 mp. 207˜213° C.                 469   N  2        1-C.sub.2 H.sub.5                                                                      H   2                                              470   N  3        1-CH.sub.3                                                                             H   3                                              471   O  2        5-CH.sub.3                                                                             H   2 mp. 151˜152° C.                 472   O  2        5-CH.sub.3                                                                             H   3                                              473   O  3        5-CH.sub.3                                                                             H   2                                              474   S  2        5-CH.sub.3                                                                             H   2                                              475   S  3        5-CH.sub.3                                                                             H   3                                              476   N  3        1-H, 5-CH.sub.3                                                                        H   3                                              477   N  3        1-H, 5-CH.sub.3                                                                        H   2                                              478   O  3        2,5-(CH.sub.3).sub.2                                                                   H   3                                              479   S  3        2,5-(CH.sub.3).sub.2                                                                   H   3                                              480   O  3        5-F      H   2                                              481   O  2        4-Cl     H   2                                              482   O  2        5-Cl     H   2 mp. 130˜131° C.                 483   O  3        5-Cl     H   3                                              484   S  3        5-Cl     H   2                                              485   N  3        1-CH.sub.3, 5-Cl                                                                       H   3                                              486   O  3        5-Br     H   2                                              487   S  2        5-Br     H   3 mp. 184˜186° C.                 488   O  2        4,5-Cl.sub.2                                                                           H   2                                              489   S  3        4,5-Cl.sub.2                                                                           H   2                                              490   S  2        4,5-Br.sub.2                                                                           H   2                                              491   O  2        5-NO.sub.2                                                                             H   2                                              492   S  2        4-NO.sub.2                                                                             H   3                                              493   S  2        5-NO.sub.2                                                                             H   2                                              494   N  3        1-CH.sub.3, 5-NO.sub.2                                                                 H   3                                              495   O  2        5-CN     H   2 mp. 212˜215° C.                 496   O  3        5-CN     H   3                                              497   S  3        5-CN     H   2                                              498   N  3        1-CH.sub.3, 5-CN                                                                       H   2                                              499   O  2        5-CF.sub.2                                                                             H   2                                              500   O  2        5-CHF.sub.2                                                                            H   3                                              501   S  3        5-CF.sub.2                                                                             H   3                                              502   N  3        1-CH.sub.3, 5-CF.sub.2                                                                 H   2                                              503   S  2        5-OCH.sub.3                                                                            H   2                                              504   O  2        5-SCH.sub.3                                                                            H   3                                              505   S  3        2,5-(SCH.sub.3).sub.2                                                                  H   2                                              506   O  2        5-SCF.sub.3                                                                            H   2 mp. 143˜144° C.                 507   O  2        5-SCF.sub.3                                                                            H   3 mp. 120˜124° C.                 508   S  2        5-CHCCl.sub.2                                                                          H   2                                              509   O  2                                                                                       ##STR359##                                                                            H   2 mp. 127˜129° C.                 510   O  2        5-COOC.sub.2 H.sub.5                                                                   H   2                                              511   S  2        5-CHO    H   2                                              512   S  2        4-CH.sub.3                                                                             CH.sub.3                                                                          2 mp. 170˜171.5° C.               __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR360##                                                                            Bonding                                                                       position of                                                          Compound the hetero-                                                          No.   Het                                                                              cycle Q.sub.l   R   m                                                __________________________________________________________________________    513   O  3     --        H   3                                                514   O  4     --        H   2                                                515   O  4     --        H   3                                                516   O  4     --        CH.sub.3                                                                          2                                                517   O  5     --        H   3                                                518   O  3     5-CH.sub.3                                                                              H   3 mp. 186˜188° C.                   519   O  5     3-CH.sub.3                                                                              H   3 mp. 200˜201° C.                   520   O  5     3-C.sub.2 H.sub.5                                                                       H   2                                                521   O  5     3-C.sub.3 H.sub.7 -iso                                                                  H   2                                                522   O  5     3-F       H   3                                                523   O  5     3-Cl      H   2                                                524   O  5     3-Br      H   2                                                525   O  5     3-OH      H   2                                                526   O  5     3-NO.sub.2                                                                              H   3                                                527   O  5     3-CN      H   3                                                528   O  5     3-CF.sub.3                                                                              H   2                                                529   O  5     3-CF.sub.3                                                                              H   3 mp. 177˜180° C.                   530   O  5     3-CHF.sub.2                                                                             H   2                                                531   O  5     3-CF.sub.2 Cl                                                                           H   2                                                532   O  5     3-CH.sub.2 Cl                                                                           H   2                                                533   O  5     3-CH.sub.2 OCH.sub.3                                                                    H   2                                                534   O  5     3-CH.sub.2 OCH(CH.sub.3).sub.2                                                          H   2                                                535   O  5     3-CCl.sub.3                                                                             H   2                                                536   O  5     3-OCH.sub.3                                                                             H   3                                                537   O  5     3-OCF.sub.3                                                                             H   2                                                538   O  4     2,5-(CH.sub.3).sub.2                                                                    H   2                                                539   S  3     --        H   3                                                540   S  4     --        H   2                                                541   S  5     --        H   2                                                542   S  3     5-CH.sub.3                                                                              H   3                                                543   S  5     3-CH.sub.3                                                                              H   2                                                544   S  5     3-F       H   2                                                545   S  3     5-Cl      H   2                                                546   S  5     3-Cl      H   2                                                547   S  3     5-Br      H   2                                                548   S  5     3-NO.sub.2                                                                              H   3                                                549   S  5     3-SCF.sub.3                                                                             H   2                                                550   N  5     1-H       H   2 mp. 190˜193° C.                   551   N  5     1-H       H   3                                                552   N  4     1-H       H   2 mp. 196˜198° C.                   553   N  4     1-H       CH.sub.3                                                                          2                                                554   N  4     1-H       H   3 mp. 222˜225° C.                   555   N  3     1-CH.sub.3                                                                              H   2 mp. 212˜215° C.                   556   N  4     1-CH.sub.3                                                                              H   2 mp. 179˜180° C.                   557   N  4     1-CH.sub.3                                                                              CH.sub.3                                                                          3                                                558   N  5     1-CH.sub.3                                                                              H   2                                                559   N  4     1-C.sub.2 H.sub.5                                                                       H   2                                                560   N  4     1-C.sub.2 H.sub.5                                                                       H   3 mp. 145˜148° C.                   561   N  4     1-C.sub.3 H.sub.7                                                                       H   3 mp. 99˜101° C.                    562   N  4     1-C.sub.3 H.sub.7 -iso                                                                  H   2                                                563   N  4     1-C.sub.3 H.sub.7 -iso                                                                  H   3 mp. 136˜137° C.                   564   N  4     1-CH.sub.2 CHCH.sub.2                                                                   H   3 mp. 109˜112° C.                   565   N  4     1-CHCCH   H   2                                                566   N  4     1-C.sub.4 H.sub.9 -tert                                                                 H   2 mp. 126˜128° C.                   567   N  4     1-C.sub. 4 H.sub.9 -tert                                                                H   3 mp. 153˜156° C.                   568   N  4                                                                                    ##STR361##                                                                             H   2 mp. 151˜153° C.                   569   N  4                                                                                    ##STR362##                                                                             H   3 Mp. 177˜180° C.                   570   N  4                                                                                    ##STR363##                                                                             H   2 mp. 111˜113° C.                   571   N  4                                                                                    ##STR364##                                                                             H   3 mp. 159˜163° C.                   572   N  4     1-CF.sub.3                                                                              H   2                                                573   N  3     1-CH.sub.2 CF.sub.3                                                                     H   2                                                574   N  4     1-CH.sub.2 CF.sub.3                                                                     H   2                                                575   N  5     1-H, 3-CH.sub.3                                                                         H   2 mp. 183˜185° C.                   576   N  5     1-H, 3-CH.sub.3                                                                         H   3                                                577   N  3     1-H, 5-Cl H   2                                                578   N  3     1-CH.sub.3, 5-F                                                                         H   2                                                579   N  3     1-CH.sub.3, 5-Cl                                                                        H   2 mp. 195˜198° C.                   580   N  3     1-CH.sub.3, 5-Cl                                                                        H   3 mp. 222˜224° C.                   581   N  3     1-C.sub.2 H.sub.5, 5-Cl                                                                 H   2                                                582   N  3     1-C.sub.3 H.sub.7 i-iso, 5-Cl                                                           H   2                                                583   N  5     1-CH.sub.3, 5-Cl                                                                        H   2                                                584   N  3     1-H, 5-CF.sub.3                                                                         H   2                                                585   N  3     1-CH.sub.3, 5-CF.sub.3                                                                  H   2                                                586   N  5     1-CH.sub.3, 5-CF.sub.3                                                                  H   2                                                587   N  4     1,3,5-(CH.sub.3).sub.3                                                                  H   3 mp. 192˜194° C.                   588   N  5     1-CH.sub.2 CF.sub.3                                                                     H   2 mp. 165˜168° C.                   __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________     ##STR365##                                                                   Compound Bonding position                                                     No.   Het                                                                              of the heterocycle                                                                     Ql        R     m                                           __________________________________________________________________________    589   O  4        --        H     2                                           590   O  5        --        H     2                                           591   O  5        --        H     3                                           592   O  4        2-CH.sub.3                                                                              H     2                                           593   O  5        2-CH.sub.3                                                                              H     2                                           594   O  5        2-CH.sub.3                                                                              H     3                                           595   O  5        4-CH.sub.3                                                                              H     2 mp. 200˜202° C.              596   O  5        4-CH.sub.3                                                                              H     3 mp. 221˜224° C.              597   O  5        2-F       H     2                                           598   O  5        2-Cl      H     2                                           599   O  5        2-Cl      H     3                                           600   O  5        2-CF.sub.3                                                                              H     2                                           601   O  5        2-SCF.sub.3                                                                             H     2                                           602   O  5        2-OCF.sub.3                                                                             H     2                                           603   O  5        2,4-(CH.sub.3).sub.2                                                                    H     2                                           604   O  2        5-COOC.sub.2 H.sub.5                                                                    H     3                                           605   S  4        --        H     2 mp. 213˜216° C.              606   S  4        --        H     3 mp. 181˜183° C.              607   S  5        --        H     2 mp. 169˜174° C.              608   S  5        --        CH.sub.3                                                                            2                                           609   S  5        --        C.sub.3 H.sub.7 -iso                                                                2                                           610   S  5        --        H     3                                           611   S  4        2-CH.sub.3                                                                              H     2 mp. 170˜172° C.              612   S  4        2-CH.sub.3                                                                              H     3 mp. 203˜206° C.              613   S  5        2-CH.sub.3                                                                              H     2 mp. 162˜166° C.              614   S  5        2-CH.sub.3                                                                              CH.sub.3                                                                            2                                           615   S  5        2-CH.sub.3                                                                              CH.sub.3                                                                            3                                           616   S  5        2-C.sub.2 H.sub.5                                                                       H     2                                           617   S  5        2-C.sub.3 H.sub.7 -iso                                                                  H     3                                           618   S  5        4-CH.sub.3                                                                              H     2                                           619   S  4        2-F       H     2                                           620   S  4        2-Cl      H     2 mp. 162˜165° C.              621   S  4        2-Cl      H     3 mp. 190˜194° C.              622   S  5        2-F       H     3                                           623   S  5        2-Cl      H     2 mp. 191˜192° C.              624   S  5        2-Cl      H     3 mp. 203˜205° C.              625   S  5        2-Cl      CH.sub.3                                                                            3                                           626   S  5        2-Cl      C.sub.2 H.sub.5                                                                     3                                           627   S  5        2,4-Cl.sub.2                                                                            H     2 mp. 179˜181° C.              628   S  4        2-NO.sub.2                                                                              H     2                                           629   S  5        2-NO.sub.2                                                                              H     3                                           630   S  4        2-CN      H     2                                           631   S  5        2-CN      H     2                                           632   S  4        2-SCH.sub.2                                                                             H     3                                           633   S  5        2-SH      H     2                                           634   S  5        2-SCH.sub.3                                                                             H     3                                           635   S  5        2-SCHF.sub.2                                                                            H     2                                           636   S  5        2-SCF.sub.2                                                                             H     2                                           637   S  5        2-SCF.sub.2 Cl                                                                          H     2                                           638   S  5        2-SCH.sub.2 CF.sub.3                                                                    H     2                                           639   S  5                                                                                       ##STR366##                                                                             H     2                                           640   S  5        2-SCN     H     2                                           641   S  4        2-NH.sub.2                                                                              H     2 mp. 165˜167° C.              642   S  4                                                                                       ##STR367##                                                                             H     2                                           643   S  4        2-OCH.sub.3                                                                             H     3                                           644   S  5        2-OCH.sub.3                                                                             H     3                                           645   S  5        2-OCF.sub.3                                                                             H     2                                           646   S  5        2-OCHF.sub.2                                                                            H     3                                           647   S  5        2-CH.sub.2 Cl                                                                           H     2                                           648   S  5        2-CHF.sub.2                                                                             H     2                                           649   S  5        2-CF.sub.3                                                                              H     2                                           650   S  5        2-CF.sub.3                                                                              H     3                                           651   S  5        2-CF.sub.2 CHF.sub.2                                                                    H     2                                           652   S  5                                                                                       ##STR368##                                                                             H     3                                           653   S  4                                                                                       ##STR369##                                                                             H     2 mp. 169˜172° C.              654   S  4                                                                                       ##STR370##                                                                             H     3 mp. 158˜159° C.              655   N  2        1-H       H     2 mp. 239˜240° C.              656   N  4        1-H       H     2                                           657   N  4        1-H       H     3 mp. 169˜173° C.              658   N  2        1-CH.sub.3                                                                              H     2 mp. 248˜252° C.              659   N  5        1-CH.sub.3                                                                              H     2                                           660   N  2                                                                                       ##STR371##                                                                             H     2 mp. 142˜145° C.              661   N  5        1-H, 4-CH.sub.3                                                                         H     2                                           662   N  4        1-H, 2-F  H     3                                           663   N  4        1-H, 2-Cl H     2                                           664   N  2        1-H, 4-NO.sub.2                                                                         H     2                                           665   N  4        1-H, 2-SCF.sub.3                                                                        H     2                                           666   N  4        1,2-(CH.sub.3).sub.2                                                                    H     2                                           667   N  4        1-CH.sub.3, 2-CF.sub.3                                                                  H     2                                           668   O  2        5-COOH    H     3                                           669   S  5        2-NHCH.sub.3                                                                            H     2                                           670   S  5        2-N(CH.sub.3).sub.2                                                                     H     3 mp. 188˜191° C.              671   S  5                                                                                       ##STR372##                                                                             H     2                                           672   S  5        2-CH.sub.2                                                                              H     4                                           673   S  2        5-CONH.sub.2                                                                            H     2                                           674   S  2        5-CONHCH.sub.3                                                                          H     2                                           675   S  2        5-CON(CH.sub.3).sub.2                                                                   H     3                                           676   S  5        2-SOCH.sub.3                                                                            H     2                                           677   S  5        2-SO.sub.2 CH.sub.3                                                                     H     2                                           678   S  5        2-N(CH.sub.3).sub.2                                                                     H     2 mp. 149˜150° C.              679   S  5        2-SCH.sub.3                                                                             H     2 mp. 150˜153° C.              680   S  5        2-Br      H     3                                           __________________________________________________________________________

                  TABLE 10                                                        ______________________________________                                         ##STR373##                                                                   Com-                                                                          pound                                                                         No.    Z                R       m                                             ______________________________________                                        681                                                                                   ##STR374##      H       2   mp. 206˜210° C.              682                                                                                   ##STR375##      H       3                                             683                                                                                   ##STR376##      H       2   mp. 265˜267° C.              684                                                                                   ##STR377##      H       2                                             685                                                                                   ##STR378##      H       3                                             686                                                                                   ##STR379##      CH.sub.3                                                                              2                                             687                                                                                   ##STR380##      H       2                                             688                                                                                   ##STR381##      H       2                                             689                                                                                   ##STR382##      H       2                                             690                                                                                   ##STR383##      H       3                                             691                                                                                   ##STR384##      H       2                                             692                                                                                   ##STR385##      H       2   mp. 221˜225° C.              693                                                                                   ##STR386##      H       2                                             694                                                                                   ##STR387##      H       2   mp. 178˜180° C.              695                                                                                   ##STR388##      H       3                                             696                                                                                   ##STR389##      H       2                                             697                                                                                   ##STR390##      H       2                                             698                                                                                   ##STR391##      H       2                                             699                                                                                   ##STR392##      H       2                                             700                                                                                   ##STR393##      H       2                                             701                                                                                   ##STR394##      H       3                                             702                                                                                   ##STR395##      CH.sub.3                                                                              2                                             703                                                                                   ##STR396##      H       2                                             704                                                                                   ##STR397##      CH.sub.3                                                                              3                                             705                                                                                   ##STR398##      H       2   mp. 188˜190° C.              706                                                                                   ##STR399##      H       3   mp. 207˜210° C.              707                                                                                   ##STR400##      H       2                                             708                                                                                   ##STR401##      H       2                                             709                                                                                   ##STR402##      H       2                                             710                                                                                   ##STR403##      H       3                                             711                                                                                   ##STR404##      H       2                                             712                                                                                   ##STR405##      H       2                                             713                                                                                   ##STR406##      H       2                                             714                                                                                   ##STR407##      H       2                                             715                                                                                   ##STR408##      H       2                                             716                                                                                   ##STR409##      H       2                                             717                                                                                   ##STR410##      H       2                                             718                                                                                   ##STR411##      H       2   mp. 163˜166° C.              719                                                                                   ##STR412##      H       2                                             720                                                                                   ##STR413##      H       3                                             721                                                                                   ##STR414##      CH.sub.3                                                                              3                                             722                                                                                   ##STR415##      H       2                                             723                                                                                   ##STR416##      CH.sub.3                                                                              2                                             724                                                                                   ##STR417##      H       2                                             725                                                                                   ##STR418##      H       3                                             726                                                                                   ##STR419##      H       3   mp. 144˜148° C.              727                                                                                   ##STR420##      H       2                                             728                                                                                   ##STR421##      H       3                                             729                                                                                   ##STR422##      H       2                                             730                                                                                   ##STR423##      H       3                                             731                                                                                   ##STR424##      H       2                                             732                                                                                   ##STR425##      H       2                                             733                                                                                   ##STR426##      H       2                                             734                                                                                   ##STR427##      H       2   mp. 142˜143° C.              735                                                                                   ##STR428##      H       2                                             736                                                                                   ##STR429##      H       3                                             737                                                                                   ##STR430##      H       2                                             738                                                                                   ##STR431##      H       2                                             739                                                                                   ##STR432##      H       2                                             740                                                                                   ##STR433##      H       3                                             741                                                                                   ##STR434##      H       2                                             742                                                                                   ##STR435##      H       2                                             743                                                                                   ##STR436##      H       2                                             744                                                                                   ##STR437##      H       2   mp. 212˜215° C.              745                                                                                   ##STR438##      H       3                                             746                                                                                   ##STR439##      H       2                                             747                                                                                   ##STR440##      H       2                                             748                                                                                   ##STR441##      H       3                                             749                                                                                   ##STR442##      H       2                                             750                                                                                   ##STR443##      H       2                                             751                                                                                   ##STR444##      H       2                                             752                                                                                   ##STR445##      H       2                                             753                                                                                   ##STR446##      H       2                                             754                                                                                   ##STR447##      H       2                                             755                                                                                   ##STR448##      H       2   m.p. 185-187° C.                   756                                                                                   ##STR449##      H       2   m.p. 216-217° C.                   757                                                                                   ##STR450##      H       3                                             758                                                                                   ##STR451##      H       2   m.p. 188-189° C.                   759                                                                                   ##STR452##      H       2   m.p. 200-203° C.                   760                                                                                   ##STR453##      H       3   m.p. 219-222° C.                   761                                                                                   ##STR454##      H       2                                             762                                                                                   ##STR455##      H       2   m.p. 259-260° C.                   763                                                                                   ##STR456##      CH.sub.3                                                                              2   m.p. 173-174° C.                   764                                                                                   ##STR457##      H       2   m.p. 216-218° C.                   765                                                                                   ##STR458##      H       2                                             766                                                                                   ##STR459##      H       2                                             767                                                                                   ##STR460##      H       3                                             768                                                                                   ##STR461##      H       2                                             769                                                                                   ##STR462##      H       3                                             770                                                                                   ##STR463##      H       2                                             771                                                                                   ##STR464##      H       3                                             772                                                                                   ##STR465##      H       2                                             773                                                                                   ##STR466##      H       2                                             774                                                                                   ##STR467##      H       2                                             775                                                                                   ##STR468##      H       2                                             776                                                                                   ##STR469##      H       2                                             777                                                                                   ##STR470##      H       3                                             778                                                                                   ##STR471##      H       2                                             779                                                                                   ##STR472##      H       2                                             780                                                                                   ##STR473##      H       2                                             781                                                                                   ##STR474##      H       2                                             782                                                                                   ##STR475##      H       2                                             783                                                                                   ##STR476##      H       2                                             784                                                                                   ##STR477##      H       3                                             785                                                                                   ##STR478##      H       2                                             786                                                                                   ##STR479##      H       2                                             787                                                                                   ##STR480##      H       2                                             788                                                                                   ##STR481##      H       3                                             789                                                                                   ##STR482##      H       2                                             790                                                                                   ##STR483##      H       2   m.p. 172-175° C.                   791                                                                                   ##STR484##      H       3                                             792                                                                                   ##STR485##      H       2                                             793                                                                                   ##STR486##      H       2                                             794                                                                                   ##STR487##      H       2                                             795                                                                                   ##STR488##      H       2                                             796                                                                                   ##STR489##      H       2                                             797                                                                                   ##STR490##      H       2                                             798                                                                                   ##STR491##      H       2                                             ______________________________________                                    

Besides table Nos. 5 to 10, there follows the case where X is N--R⁷ :(table 11)

    TABLE 11      ##STR492##       Comp. No. Z R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 n     R.sup.7 Y                    799      ##STR493##      H H H -- -- H H 0 H N      800     ##STR494##      CH.sub.3 H H -- -- H H 0 H N      801     ##STR495##      H H H H H H H 1 H N      802     ##STR496##      H H H H H H H 1 H N      803     ##STR497##      H H H H H H H 1 H N      804     ##STR498##      H H H H H H H 1 H N      805     ##STR499##      H H H -- -- H H 0 H N mp. 149-150` C.      806     ##STR500##      H H H -- -- H H 0 H N      807     ##STR501##      H H H -- -- H H 0 H N      808     ##STR502##      H H H H H H H 1 H N      809     ##STR503##      H H H -- -- H H 0 H N      810     ##STR504##      H H H -- -- H H 0 H N      811     ##STR505##      H H H H H H H 1 H N      812     ##STR506##      H H H -- -- H H 0 H N      813     ##STR507##      H H H H H H H 1 H N mp. 123-128° C.      814     ##STR508##      H H H H H H H 1 H N      815     ##STR509##      H H H H H H H 1 H N      816     ##STR510##      H H H H H H H 1 H N      817     ##STR511##      H H H H H H H 1 H N      818     ##STR512##      H H H -- -- H H 0 H N mp. 141-145° C.      819     ##STR513##      H H H H H H H 1 H N      820     ##STR514##      H H H H H H H 1 H N      821     ##STR515##      H H H H H H H 1 H N      822     ##STR516##      H H H H H H H 1 H N      823     ##STR517##      H H H -- -- H H 0 H N      824     ##STR518##      CH.sub.3 H H -- -- H H 0 H N      825     ##STR519##      H H H -- -- H H 0 H N      826     ##STR520##      H H H -- -- H H 0 H N      827     ##STR521##      H H H -- -- H H 0 H N mp. 181-183° C.      828     ##STR522##      H H H H H H H 1 H N      829     ##STR523##      H H H -- -- H H 0 H N      830     ##STR524##      H H H -- -- H H 0 H N      831     ##STR525##      H H H -- -- H H 0 H N mp. 142- 144° C.      832     ##STR526##      H H H -- -- H H 0 H N      833     ##STR527##      H H H -- -- H H 0 H N mp. 216-219° C.      834     ##STR528##      H H H -- -- H H 0 H N      835     ##STR529##      H H H CH.sub.3 CH.sub.3 H H 1 H CH mp. 210-213° C.      836     ##STR530##      H H H H H H H 1 CH.sub.3 CH      837     ##STR531##      H H H H H H H 1 C.sub.2 H.sub.5 CH      838     ##STR532##      H H H -- -- H H 0      ##STR533##      CH      839     ##STR534##      H H H -- -- H H 0      ##STR535##      CH      840     ##STR536##      H H H -- -- H H 0      ##STR537##      CH      841     ##STR538##      H H H -- -- H H 0      ##STR539##      CH mp. 154-156° C.      842     ##STR540##      H H H H H H H 1      ##STR541##      CH glass      843     ##STR542##      H H H -- -- H H 0      ##STR543##      CH n.sub.D.sup.20 1.5980      844     ##STR544##      H H H H H H H 1      ##STR545##      CH      845     ##STR546##      H H H H H H H 1      ##STR547##      CH      846     ##STR548##      H H H -- -- H H 0      ##STR549##      CH      847     ##STR550##      H H H -- -- H H 0      ##STR551##      CH      848     ##STR552##      H H H -- -- H H 0 H CCOOC.sub.2 H.sub.5 mp. 153-155° C.  849      ##STR553##      H H H H H H H 1 H      ##STR554##      850     ##STR555##      H H H H H H H 1 H      ##STR556##      851     ##STR557##      H H H H H H H 1 H CCO(CH.sub.2).sub.3 CH.sub.3      852     ##STR558##      H H H -- -- H H 0 H      ##STR559##      853     ##STR560##      H H H -- -- H H 0 CH.sub.3 N      854     ##STR561##      H H H -- -- H H 0 C(CH.sub.3).sub.3 N      855     ##STR562##      H H H H H H H 1 CH.sub.2 SCH.sub.3 N      856     ##STR563##      H H H H H H H 1 CH.sub.2 CH.sub. 2 OC.sub.2 H.sub.5 N      857     ##STR564##      H H H -- -- H H 0 CH.sub.2 COCH.sub.3 N      858     ##STR565##      H H H -- -- H H 0 COCH.sub.3 N      859     ##STR566##      H H H H H H H 1 CHO N      860     ##STR567##      H H H H H H H 1 COCH.sub.3 N      861     ##STR568##      H H H -- -- H H 0 CON(C.sub.2 H.sub.5).sub.2 N      862     ##STR569##      H H H -- -- H H 0      ##STR570##      N      863     ##STR571##      H H H -- -- H H 0 COCH.sub.3 N mp. 134-136° C.      864     ##STR572##      H H H -- -- H H 0      ##STR573##      N      865     ##STR574##      H H H -- -- H H 0      ##STR575##      N      866     ##STR576##      H H H -- -- H H 0      ##STR577##      N      867     ##STR578##      H H H -- -- H H 0 COOC.sub.2 H.sub.5 N      868     ##STR579##      H H H H H H H 1      ##STR580##      N      869     ##STR581##      H H H -- -- H H 0      ##STR582##      N      870     ##STR583##      H H H -- -- H H 0      ##STR584##      N mp. 156-158° C.      871     ##STR585##      H H H H H H H 1      ##STR586##      N      872     ##STR587##      H CH.sub.3 H -- -- H H 0 H CH      873     ##STR588##      H H H -- -- H H 0 H      ##STR589##      874     ##STR590##      H H H -- -- H H 0 H      ##STR591##      875     ##STR592##      H H H -- -- H H 0 CH.sub.3 N      876     ##STR593##      H H H -- -- H H 0 COCH.sub.2 OCH.sub.3 N      877     ##STR594##      H H H -- -- H H 0      ##STR595##      N      878     ##STR596##      H H H -- -- H H 0      ##STR597##      N      879     ##STR598##      H H H -- -- H H 0      ##STR599##      N      880     ##STR600##      H H H -- -- H H 0      ##STR601##      N      881     ##STR602##      H H H -- -- H H 0      ##STR603##      N

The case where the formula (I) represents the following formula: (table12) ##STR604##

                                      TABLE 12                                    __________________________________________________________________________    Comp.                                                                         No. Z        R R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         n L Hal                                            __________________________________________________________________________    882                                                                                ##STR605##                                                                            H H H --                                                                              --                                                                              H H 0 Cl                                                                              Cl                                             883                                                                                ##STR606##                                                                            H H H --                                                                              --                                                                              H H 0 Cl                                                                              Cl                                             884                                                                                ##STR607##                                                                            H H H --                                                                              --                                                                              H H 0 Br                                                                              Br mp. 140-143° C. (decomp.)            885                                                                                ##STR608##                                                                            H H H --                                                                              --                                                                              H H 0 Cl                                                                              Br                                             __________________________________________________________________________

The case where the formula (I) represents the following formula: (table13)

                  TABLE 13                                                        ______________________________________                                        Comp.                                                                         No.   Compounds                                                               ______________________________________                                        886                                                                                  ##STR609##             mp. 170-175° C. (decomp.)                887                                                                                  ##STR610##                                                             ______________________________________                                    

Typical examples of synthesizing the intermediate compound of theformula (II) are shown below.

Example 36 ##STR611##

Trimethylenediamine (37 g) was dissolved in 120 ml of acetonitrile, anda solution of 14.8 g of 5-chloromethyl-2-methylthiazole in 30 ml ofacetonitrile was added dropwise at 10° to 15° C. After the addition, themixture was stirred at 30° to 40° C. for a while, and then 8 g of a 50%aqueous solution of sodium hydroxide was added. Subsequently, thevolatile materials were removed at a bath temperature of less than 50°C. under 5 mmHg. The inorganic materials were removed from the residueby filtration to give 16.7 g ofN-(2-methyl-5-thiazolylmethyl)trimethylenediamine (purity about 90%) asa colorless oil.

n_(D) ²² : 1.5126.

Example 37 ##STR612##

Ethylenediamine (30 g) was dissolved in 120 g of acetonitile, and asolution of 17.6 g of 5-bromomethyl-3-methylisoxazole in 30 ml ofacetonitrile was added dropwise at 5° to 10° C. After the addition, themixture was stirred for 1 hour with a care taken not to permit thetemperature of the reaction system to rise above 20° C. Then, most ofthe volatile materials were removed under vacuum (less than 2 mmHg)while maintaining the bath temperature at 20° C. Ice water was added tothe residue, and the mixture was extracted with dichloromethane. Thedichloromethane layer was dehydrated, and dichloromethane was distilledoff under reduced pressure to give 10.0 g ofN-(3-methyl-5-isoxazolylmethyl)ethylenediamine (purity about 95%) as acolorless oil.

NMR spectrum (δ in CDCl₃): NH, NH₂ : 1.47 (ppm); --CH₂ CH₂ --: 2.23;--CH₃ : 2.7; --CH₂ : 5.8; Hetero-H: 5.9.

Example 38 ##STR613##

At room temperature 11 g of 1-methyl-4-pyrazole carbaldehyde was slowlyadded to 37 g of ethylenediamine in 150 ml of dry acetonitrile.Molecular sieves 4A (a product of Wako Pure Chemicals, Co.) were addedas a dehydrating agent to the solution. The mixture was stirred at roomtemperature for 2 hours, and filtered. Acetonitrile was distilled offunder reduced pressure from the filtrate. To the residue was added 100ml of ethanol, and then 4 g of sodium borohydride was added little bylittle at room temperature. The mixture was then stirred at roomtemperature for 2 hours, and ethanol was distilled off under reducedpressure. Water was added to the residue, and the mixture was extractedwith dichloromethane. The solvent was distilled off from thedichloromethane layer, and the residue was vacuum-distilled to give 10 gof N-(1-methyl-4-pyrazolylmethyl)trimethylenediamine as a colorless oil.

bp.: 120°-125° C./0.8 mmHg.

Example 39 ##STR614##

A solution composed of 12.6 g of 3-acetylthiophene, 30 g ofethylenediamine and 150 ml of benzene was refluxed with stirring whileremoving water as an azeotrope. When formation of water was no longerobserved, benzene was distilled off under reduced pressure. Ethanol (100ml) was added to the residue, and subsequently, 4 g of sodiumborohydride was added little by little. The mixture was then stirred at40° C. for 2 hours. Ethanol was distilled off under reduced pressure. Asmall amount of the inorganic matter was removed from the residue.Subsequent vacuum distillation have 8.2 g ofN-[1-(3-thienyl)ethyl]ethylenediamine.

bp.: 102°-105° C./3.5 mmHg.

Novel compounds of the formula (II) obtained by the same methods asdescribed in Examples 36 to 39 are shown below.

                  TABLE 14                                                        ______________________________________                                         ##STR615##                                                                   Z                R       m                                                    ______________________________________                                         ##STR616##      H       3                                                     ##STR617##      H       2     n.sub.D.sup.20 1.5523                           ##STR618##      H       3     n.sub.D.sup.20 1.5495                           ##STR619##      H       3                                                     ##STR620##      H       2     bp 108˜110° C./ 4 mmHg             ##STR621##      H       3     bp 135˜140° C./ 0.5 mmHg           ##STR622##      H       2                                                     ##STR623##      H       2     n.sub.D.sup.20 1.4775                           ##STR624##      H       3     n.sub.D.sup.25 1.4752                           ##STR625##      H       3                                                     ##STR626##      H       3                                                     ##STR627##      H       3                                                     ##STR628##      H       3                                                     ##STR629##      H       3     n.sub.D.sup.20 1.4683                           ##STR630##      H       2                                                     ##STR631##      H       3                                                     ##STR632##      H       2     n.sub.D.sup.20 1.5335                           ##STR633##      H       3     n.sub.D.sup.20 1.5230                           ##STR634##      H       2                                                     ##STR635##      H       3                                                     ##STR636##      H       2     bp 125˜127° C./ 1 mmHg             ##STR637##      CH.sub.3                                                                              2     bp 133˜135° C./ 1.2 mmHg           ##STR638##      H       3     n.sub.D.sup.20 1.5251                           ##STR639##      H       3                                                     ##STR640##      H       3     n.sub.D.sup.20 1.5085                           ##STR641##      H       2     n.sub.D.sup.20 1.5045                           ##STR642##      H       2     n.sub.D.sup.20 1.4651                           ##STR643##      H       2                                                     ##STR644##      H       2     n.sub.D.sup.20 1.4940                           ##STR645##      H       3     n.sub.D.sup.20 1.4904                           ##STR646##      H       3                                                     ##STR647##      H       2     n.sub.D.sup.25 1.5003                           ##STR648##      H       3                                                     ##STR649##      H       2     n.sub.D.sup.27 1.5160                           ##STR650##      H       3     n.sub.D.sup.27 1.5130                           ##STR651##      H       2     n.sub.D.sup.20 1.5722                           ##STR652##      H       2                                                     ##STR653##      H       3                                                     ##STR654##      H       2     n.sub.D.sup.24 1.5205                           ##STR655##      H       2     n.sub.D.sup.24 1.5691                           ##STR656##      H       3                                                     ##STR657##      H       2                                                     ##STR658##      H       2                                                     ##STR659##      H       2     n.sub.D.sup.20 1.5788                           ##STR660##      H       3                                                     ##STR661##      H       2                                                     ##STR662##      H       2                                                     ##STR663##      H       2                                                     ##STR664##      H       2     n.sub.D.sup.20 1.5457                           ##STR665##      H       2                                                     ##STR666##      H       3                                                     ##STR667##      H       2                                                     ##STR668##      H       3     bp 90° C./2.5 mmHg                       ##STR669##      H       2     n.sub.D.sup.17 1.4715                           ##STR670##      H       2                                                     ##STR671##      H       2                                                    ______________________________________                                    

Example 40 ##STR672##

A solution composed of 6-chloronicotinaldehyde (14.2 g),2-aminoethanethiol (7.7 g) and benzene (80 ml) was heated with stirringfor 5 hours while removing water as an azeotrope. After the reaction,benzene was distilled off under reduced pressure, and further volatilematerials were removed at 1 mmHg and 70° C. to give2-(2-chloro-5-pyridyl)thiazolidine (18 g) as a residue. Ten grams of2-(2-chloro-5-pyridyl)thiazolidine was dissolved in 100 ml of ethanol,and sodium borohydride was added. With stirring, the mixture wasgradually heated and thereafter refluxed for 1 hour. Ethanol wasdistilled off under reduced pressure, and chloroform was added to theresidue. Insoluble materials were separated by filtration and thechloroform layer was washed with water and dehydrated. Chloroform wasdistilled off under reduced pressure to give the desiredN-(2-chloro-5-pyridylmethyl)2-aminoethanediol (8.3 g).

n_(D) ²⁴ : 1.5917.

Example 41 ##STR673##

A solution composed of 6-methylnicotinaldehyde (12.1 g,3-aminopropanethiol (9.1 g) and benzene (120 ml) was refluxed for 5hours with stirring while removing water as an azeotrope. After thereaction, benzene was distilled off under reduced pressure, and volatilematerials were removed at 1 mmHg and 70° C. As a residue,3-pyridyltetrahydrothiazine (16.5 g) was obtained. Then,3-pyridyltetrahydrothiazine (10 g) was dissolved in 100 ml of ethanol,and sodium borohydride was added. The mixture was gradually heated withstirring, and subsequently refluxed for 1 hour. Ethanol was distilledoff under reduced pressure. Chloroform was added to the residue, andinsoluble materials were separated by filtration. The chloroform layerwas washed with water and dehydrated. On distilling off chloroform underreduced pressure, the desired N-(3-pyridyl)3-aminopropanethiol (6.2 g)was obtained.

n_(D) ²⁰ : 1.5733.

Compound No. II of the following formula was also prepared by the samemethod as in Examples 40 and 41. ##STR674##

Example 42 ##STR675##

Ethylenediamine (60 g) was dissolved in benzene (200 ml), and5-formylpyrimidine (21.6 g) was added at room temperature. Subsequently,the mixture was heated, and refluxed for 3 hours while removing water asan azeotrope. After the reaction, benzene and the excess ofethylenediamine were distilled off under reduced pressure. The residuewas dissolved in ethanol (200 ml). Sodium borohydride (8.4 g) was addedportionwise to this solution at room temperature, and subsequently themixture was stirred at room temperature for 5 hours. Ethanol wasdistilled off under reduced pressure. Dichloromethane (100 ml) was addedto the residue, and a dichloromethane-soluble portion was separated.Dichloromethane was distilled off from the dichloromethane layer underreduced pressure to give N-(5-pyrimidinylmethyl)ethylenediamine (25.8 g)as a colorless oil. n_(D) ²⁵ =1.5532.

Example 43 ##STR676##

Ethylenediamine (30 g) was dissolved in acetonitrile (200 ml), andpyrazinylmethyl chloride (12.9 g) was added dropwise to this solution at5° to 10° C. After addition, the mixture was stirred at room temperaturefor 1 hour. Then, a 50% aqueous solution of sodium hydroxide (8 g) wasadded, and thereafter, volatile materials were removed at a bathtemperature of 60° C. under 5 mmHg. The inorganic salt was then removedby filtration. Thus, N-(pyrazinylmethyl)ethylenediamine (14.1 g) wasobtained as a colorless oil. n_(D) ²⁰ =1.5359.

Example 44 ##STR677##

A solution of 2-cyano-5-pyridylmethyl chloride (4.6 g) in acetonitrile(20 ml) was added dropwise to a solution of ethylenediamine (9 g) inacetonitrile (50 ml) at 5° to 10° C. After the addition, the mixture wasstirred at room temperature for 3 hours. Acetonitrile and the excess ofethylenediamine were distilled off under reduced pressure from thereaction mixture. Dichloromethane was added to the residue, and aportion of it soluble in dichloromethane was separated. Volatilematerials were removed at 50° C. and 1 mmHg to giveN-(2-cyano-5-pyridylmethyl)ethylenediamine (4.5 g) as a colorless oil.

n_(D) ²⁰ =1.5718.

Example 45 ##STR678##

5-Trifluoromethylpicoline aldehyde (3.5 g) was added dropwise at roomtemperature to a solution of trimethylenediamine (7.4 g) in benzene (70ml). After the addition, the mixture was gradually heated with stirring,and then while separating water as an azeotrope, refluxed for 2 hours.Benzene was distilled off under reduced pressure, and then the residuewas dissolved in ethanol (100 ml). With stirring at 10° to 15° C.,sodium borohydride (0.9 g) was added little by little. The mixture wasthen stirred at room temperature for 2 hours. Ethanol was distilled offat less than 30° C. Dichloromethane was added to the residue, and aportion of it soluble in dichloromethane was separated. Dichloromethanewas distilled off under reduced pressure, and volatile materials wereremoved at 1 mmHg and less than 60° C. to giveN-(5-trifluoromethyl-2-pyridylmethyl)trimethylenediamine (3.5 g) as acolorless oil.

n_(D) ²⁰ 1.4651.

Example 46 ##STR679##

A solution of 8.1 g of 2-chloro-5-chloromethylpyridine in 30 ml ofacetonitrile was added dropwise to a mixture of 14.8 g of1,2-diaminopropane, 5 g of 40% sodium hydroxide solution, and 100 ml ofacetonitrile at 0° C. during 2 hours with vigorous stirring. Afterstirring for a short time at room temperature, the acetonitrile, waterand excess 1,2-diaminopropane were removed under reduced pressure.Inorganic salt was filtered off with suction from the residue. Thefiltrate was the desired product,2-amino-1-(2-chloro-5-pyridylmethylamino)propane (9.3 g).

n_(D) ¹⁷ 1.5450.

In the same way as in Example 46, the following compounds were produced.

N-methyl-N'-3-pyridylmethylethylenediamine

bp. 140° C./2.5 mmHg

2-amino-2-methyl-1-(3-pyridylmethylamino)propane

bp. 115° C./1.5 mmHg

2-aminomethyl-2-methyl-1-(1-methyl-4-pyrazolylmethyl)propane

n_(D) ²⁵ 1.5109.

Example 47 ##STR680##

A solution of 18.6 g of N-(2-chloro-5-pyridylmethyl) ethylenediamine, 11g of 1-methylpyrazole-4-carbaldehyde in 150 ml of benzene was stirred onwarm water bath. After a short time, water was separated from thesolution and the Schiff base was obtained. The benzene and water werethen removed under reduced pressure and 100 ml of ethanol was added tothe residue. To the solution 3.8 g of sodiumborohydride was addedportionwise at room temperature and the mixture was stirred for 1 day.After removing the ethanol under reduced pressure, the residue wasdissolved in dichloromethane and washed with water. The treatment ofdichloromethane solution the usual way gave the desired intermediate,N-(2-chloro-5-pyridylmethyl)-N'-(1-methyl-4-pyrazolylmethyl)ethylenediamineas a viscous oil. The yield was 23.5 g.

n_(D) ²⁰ 1.5655.

In the same way as in Example 47, the following compounds, for example,were produced.

N-(3-pyridylmethyl)-N'-(2-chloro-5-pyridylmethyl)ethylenediamine

n_(D) ²⁰ 1.5846

N-(3-methyl-5-isoxazolylmethyl)-N'-(1-methyl-4-pyrazolymethyl)trimethylenediamine

n_(D) ²⁰ 1.5224

Example 48 ##STR681##

A solution of 7 of 5-bromomethyl-3-methylisoxazole in 20 ml ofacetonitrile was added dropwise to a solution of 12.2 g of2-aminoethanol in 100 ml of acetonitrile below 10° C. After stirring fora while at room temperature, the acetonitrile and excess-2-aminoethanolwere removed under reduced pressure. Chloroform was added to theresidue, and it was washed with a small quantity of water. The treatmentof the chloroform solution the usual way gave the desired2-(2-methyl-5-isoxazolylmethylamino)ethanol. The yield was 4.4 g.

n_(D) ²⁰ 1.5130.

In the same way as in Example 48, the following compounds, for example,were produced.

3-(2-chloro-5-pyridylmethylamino)propanol

n_(D) ²⁷ 1.5391

N-(4-pyridylmethyl)ethanolamine

bp. 148°-150° C./3 mmHg

Example 49 ##STR682##

To a solution of 15.6 g of 2-(3-methyl-5-isoxazolylmethylamino)ethanolin 100 ml of chloroform was added catalytic pyridine and then 15 g ofthionylchloride at room temperature. After the addition, the mixture wasrefluxed for 30 minutes, and the evaporation of volatile material invacuum yielded crude chlorinated compound as its hydrochloride.

mp. 136°-139° C.

An ethanolic potassium hydrosulfide solution was prepared by saturatinghydrogen sulfide gas in a solution of 13.4 g of potassium hydroxide in120 ml of ethanol. To the resulting solution was added portionwise theabove chloride hydrochloride at 25°-30° C. with stirring. The reactionmixture was warmed up slowly, then was stirred for 2 hours at 60° C.After cooling to room temperature, inorganic salt was quickly filteredoff with suction. The solvent was removed from the filtrate underreduced pressure to give 2-(3-methyl-5-isoxazolylmethylamino)ethanethiol(12.9 g) as an oil.

n_(D) ²⁵ 1.5490.

In the same way as in Example 49, the following compound, for example,was produced.

2-(2-methyl-5-pyrazinylamino)ethylmercaptan

n_(D) ²⁸ 1.5581

Example 50 ##STR683##

2.72 g of ethylenetrithiocarbonate and 2.52 g of dimethylsulfate weremixed and heated to 100° C. for 1 hour. 10 ml of acetic acid and 2.02 gof triethylamine were added to the resulting2-methylmercapto-1,3-dithiolaniummethylsulfate. 2.6 g of2,2,2-trifluoronitroethane was then added dropwise to the mixture withcooling in an ice bath. The whole mixture was heated slowly to 100° C.and maintained at this temperature for 4 hours. After standing overnightat room temperature, 100 ml of water was added to the reaction mixture.The precipitated crystal was filtered and recrystallized from ethanol togive 1-nitro-2,2-ethylenedimercapto-1-trifluoromethylethylene. The yieldwas 4.35 g.

mp. 130°-133° C.

Example 51 ##STR684##

To a solution of 13.1 g of 1-nitro-2-pentanone in 200 ml ofdimethylfulfoxide was added dropwise 44 g of 20% sodium hydroxidesolution at 10°-20° C. 12 g of carbon disulfide was then added dropwiseto the solution at 10° C. and the mixture was stirred for 2 hours at0°-10° C. 57 g of methyliodide was dropped into the mixture with icecooling and the reaction mixture was allowed to stand overnight at roomtemperature. This was then poured into ice water and the organic layerwas extracted with dichloromethane. The extract was washed with water afew times, and after removing the solvent the residue was purified bychromatography on a silica gel column to give desired1-butyroyl-1-nitro-2,2-bis (methylthio)ethylene. The yield is 3.0 g.

n_(D) ²² 1.5880.

In the same was as in Example 51, the following compound, for example,was produced.

1-benzenesulfonyl-1-nitro-2,2-bis(methylthio) ethylene

n_(D) ²⁰ 1.5868

Example 52 ##STR685##

2.5 g of sodium hydride 60% in oil was added in small portions to asolution of 3.9 g of 2-nitroiminoimidazolidine in dry dimethylformamide.After the addition, the mixture was stirred until the generation ofhydrogen gas ceased. The mixture was cooled at -5° C. and 4.7 g ofphenyl chloroformate was added dropwise below 0° C. After stirring for 1hour at room temperature, the reaction mixture was poured into icewater, adjusted to pH 7, and extracted with dichloromethane. The whitecrystals which remained after removing the dichloromethane, and washingwith ether were 1-(phenoycarbonyl)-2-nitroiminoimidazolidine and weighed5.1 g.

mp. 171°-175° C.

In the same way as in Example 52, the following compounds, for example,were produced.

1-(2-methyl-5-nitrobenzenesulfonyl)-2-(nitroimino) imidazolidine

mp. 193°-197° C.

1-(2,4-dichlorobenzoyl)-2-(nitroimino)imidazolidine

mp. 184°-186° C.

Example 53 ##STR686##

A solution of 3.9 g of 2-nitroiminoimidazolidine and 4.6 g of3-chlorophenylisocyanate in 80 ml of dry acetonitrile was refluxed for 3hours. After cooling to room temperature, the precipitated crystals werefiltered, and washed with ether to give desired1-(3-chlorophenylcarbamoyl)-2-nitroiminoimidazolidine. The yield was 4.7g.

mp. 214°-216° C.

USE EXAMPLE ##STR687## Example 54

Test on Nephotettix cincticeps having resistance to organophosphorusagents:

Preparation of a Test Chemical

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoyethylene alkyl phenyl ether

To form a suitable preparation, 1 part by weight of the active compoundwas mixed with the aforesaid amount of the solvent containing theaforesaid amount of the emulsifier. The mixture was diluted with waterto a predetermined concentration.

Testing Method

Onto rice plants, about 10 cm tall, planted in pots each having adiameter of 12 cm was sprayed 10 ml per pot of the water-dilution ofeach active compound in a predetermined concentration prepared as above.The sprayed chemical was dried, and a wire net having a diameter of 7 cmand a height of 14 cm was put over each pot, and 30 female imagoes ofNephotettix cincticeps showing resistance to organophosphorus agentswere released into the net. The pots were each placed in a constanttemperature chamber and the number of dead insects was examined 2 dayslater, and the kill ratio was calculated.

As the result, for instance, Compound Nos. 1, 2, 3, 4, 5, 6, 8, 9, 10,11, 13, 14, 15, 16, 17, 19, 20, 22, 26, 27, 31, 32, 33, 34, 35, 36, 39,65, 66, 75, 76, 105, 164, 290, 304, 323, 336, 340, 396, 409, 431, 444,453, 518, 612, 623, 624, 705, 706, 755, 762, 813, 831, 884 showed 100%kill at 8 ppm A.I.

On the other hand, as comparison,

A-1 showed 65% kill at 40 ppm A.I.,

A-2 40% kill at 200 ppm A.I. and 0% kill at 40 ppm A.I.,

A-3 0% kill at 200 ppm A.I., and

A-4 30% kill at 200 ppm A.I.

Example 55

Test on planthoppers:

Testing Method

A water dilution in a predetermined concentration of the active compoundprepared as in Example 54 was sprayed onto rice plants, about 10 cmtall, grown in pots with a diameter of 12 cm in an amount of 10 ml perpot. The sprayed chemical was dried, and a wire net, 7 cm in diameterand 14 cm tall, was put over each of the pots. Thirty female imagoes ofNilaparvata lugens Stal of a strain which showed resistance toorganophosphorus chemicals were released into the net. The pots wereleft to stand in a constant temperature chamber and the number of deadinsects was examined two days later. The kill ratio was then calculated.

In the same way as above, the kill ratio was calculated on Sogatellafurcifera Horvath and organophosphorus-resistant Laodelphax striatellusFallen.

As the result, for instance, Compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 29, 35, 37, 39, 43, 65,70, 75, 79, 146, 164, 230, 303, 308, 324, 331, 350, 396, 409, 424, 453,518, 529, 550, 556, 579, 612, 623, 624, 649, 701, 705, 706, 755, 756,758, 848 showed 100% kill at 40 ppm A.I. against each planthopper.

On the other hand, as comparison, A-1 showed, at 40 ppm A.I., 50% killagainst N. lugens, 40% kill against S. furcifera and L. striatellus, A-2at 200 ppm A.I. 30% kill against N. lugens, 20% kill against L.striatellus and 50% kill against S. furcifera, and at 40 ppm A.I. 0%kill against each planthopper, A-3 at 200 ppm A.I. 0% kill against eachplanthopper, and A-4 at 200 ppm A.I. 100% kill ratio against N. lugens,0% kill against L. striatellus and S. furcifera.

Example 56

Test on Myzus persicas (green peach aphids) having resistance toorganophosphorus chemicals and carbamate chemicals:

Testing Method

Green peach aphids which had been bred and had resistance toorganophosphorus chemicals and carbamate chemicals were inoculated oneggplant seedlings (black elongate eggplants), about 20 cm tall, grownin unglazed pots having a diameter of 15 cm (about 200 aphids perseedling). One day after the inoculation, a water dilution of eachactive compound at a predetermined concentration prepared as in Example54 was sprayed in a sufficient amount onto the plants using a spray gun.After the spraying, the pots were left to stand in a greenhouse at 28°C. Twenty-four hours after the spraying, the kill ratio was calculated.For each compound, the test was carried out through two replicates.

As the results, for instance, compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28,29, 30, 31, 32, 33, 35, 71, 74, 75, 98, 105, 164, 230, 231, 373, 396,409, 518, 529, 550, 556, 579, 612, 623, 624, 649, 705, 706, 755, 756,758, 763, 831 showed 100% kill at 200 ppm A.I.

On the other hand, A-1 showed 80% kill at 1000 ppm A.I. and 30% kill at200 ppm A.I., A-3 60% kill at 1000 ppm A.I. and 0% kill at 200 ppm A.I.,and A-4 60% kill at 1000 ppm A.I., 0% kill at 200 ppm A.I..

Examples 54, 55 and 56 are typical examples of insecticidal uses, andthe compounds of this invention exemplified herein are also typicalexamples. It should be understood that the present invention is not tobe limited to them alone.

We claim:
 1. A compound formula ##STR688## in which R¹, R², R⁵ and R⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R³ and R⁴ independently represent a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms,R⁷ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atoms which may be substituted by at least one member selected from the class consisting of alkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, a dimethylamino group and trimethylsilyl, an alkenyl group having 2 to 3 carbon atoms which may be substituted by a chlorine atom, an alkynyl group having 2 to 3 carbon atoms, a benzyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom and a nitro group, a formyl group, an alkenylcarbonyl group having an alkenyl with 2 to 3 carbon atoms, an alkyl carbonyl group having 1 to 5 carbon atoms which may be substituted by at least one member selected from the class consisting of a methoxy group, a phenoxy group, a fluorine, chlorine and bromine atom, a benzoyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, a difluoromethoxy group, a trifluoromethoxy group and a nitro group, a benzylcarbonyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom and a bromine atom, an alkoxycarbonyl group having an alkyl with 1 to 4 carbon atoms which may be substituted by a fluorine atom and/or a chlorine atom, an alkylthiocarbonyl group having an alkyl with 1 to 4 carbon atoms, a phenoxycarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a phenylthiocarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a benzyloxycarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom, and a bromine atom, a benzoylaminocarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a phenylsulfonylaminocarbonyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom and a bromine atom, a phenylthio group, an alkylsulfonyl group which may be substituted by a fluorine atom and/or a chlorine atom, a phenylsulfonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom, a bromine atom and a nitro group, a methylcarbonylmethyl group, a phenacyl group which may be substituted by a fluorine atom and/or a chlorine atom, an organophosphono group, an organothionophosphono group, --CH₂ --W or --CO--W; W represents a 5 to 6 membered hetercyclic group, containing one or two hetero atoms selected from the class consisting of an oxygen atom, a sulfur atom and a nitrogen atom, which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom and alkyl groups having 1 to 4 carbon atoms, Y represents a nitrogen atom or the following ##STR689## R⁹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atoms which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group having 1 to 2 carbon atoms, alkylthio groups having 1 to 2 carbon atoms, a cyano group, a dimethylamino group, alkylcarbonyl groups having an alkyl with 1 to 2 carbon atoms and alkoxycarbonyl groups having an alkyl with 1 to 2 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a phenyl group, an alkylcarbonyl group having an alkyl with 1 to 4 carbon atoms which may be substituted by at least one member selected from the class consisting of a methoxy group, a chlorine atom and a fluorine atom, an alkenylcarbonyl group having an alkenyl with 2 to 3 carbon atoms, a benzoyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom, a methoxy group and a methyl group, an alkoxycarbonyl group which may be substituted by a fluorine atom and/or a chlorine atom, an alkylthiocarbonyl group having an alkyl with 1 to 4 carbon atoms, a phenoxycarbonyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group and a nitro group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, a benzoylaminocarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a phenylsulfonylaminocarbonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, an alkylsulfonylaminocarbonyl group having an alkyl with 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group which may be substituted by a fluorine atom and/or a chlorine atom, a phenylthio group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, or a phenylsulfonyl group which may be substituted by at least one member selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, in addition, R⁹ may form a bis-form of the formula (I), via a methylene group, R represents a hydrogen atom or a methyl group, and Z represents a 5 to 6 membered heterocyclic group, containing one to three hetero atoms selected from the class consisting of an oxygen atom, a sulfur atom and a nitrogen atom, at least one of which is a nitrogen atom, which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom, alkyl groups having 1 to 4 carbon atoms which may be substituted by a fluorine atom and/or a chlorine atom, a nitro group, a cyano group, alkylsulfinyl groups having 1 to 4 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms which may be substituted by a fluorine atom and/or a chlorine atom, alkylthio groups having 1 to 4 carbon atoms which may be substituted by a fluorine atom and/or a chlorine atom; alkenyl groups having 2 to 3 carbon atoms which may be substituted by a chlorine atom, an acetamide group which may be substituted by a fluorine atom and/or a chlorine atom, alkoxycarbonyl groups having an alkyl with 1 to 4 carbon atoms, a thiocyanato group, alkynyl groups having 2 to 4 carbon atoms, an amino group, a methylamino group, a dimethylamino group, an acetyl group, a formyl group, a carboxy group, a hydroxy group, a mercapto group, cycloalkyl groups having 3 to 7 carbon atoms, an oxo group, a thioxo group, alkenylthio groups substituted by a fluorine atom, a chlorine atom and/or a bromine atom, alkoxyalky groups having 2 to 4 carbon atoms in total, alkylaminocarbonyl groups having an alkyl with 1 to 2 carbon atoms, dialkylaminocarbonyl groups having an alkyl with 1 to 2 carbon atoms, a phenyl group, a phenoxy group and a benzyl group, provided that where R¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneously, and Y represents ##STR690## then Z does not represent a pyridyl group which may optionally be substituted.
 2. A compound according to claim 1, in whichR¹, R², R⁵ and R⁶ independently represent a hydrogen atom or a methyl group, R³ and R⁴ independently represent a hydrogen atom or a methyl group, R⁷ represents a hydrogen atom, an alkyl group which may be substituted by at least one member selected from the class consisting of a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a cyano group, a fluorine atom, a chlorine atom and a trimethylsilyl group, an allyl group which may be substituted by a chlorine atom, a propargyl group, a benzyl group which may be substituted by a methyl group and/or a chlorine atom, a formyl group, a vinylcarbonyl group, an alkylcarbonyl group having an alkyl with 1 to 3 carbon atoms which may be substituted by at least one member selected from the class consisting of a methoxy group, a phenoxy group and a chlorine atom, a benzoyl group which may be substituted by at least one member selected from the class consisting of a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group and a nitro group, a benzylcarbonyl group which may be substituted by a chlorine atom, an alkoxycarbonyl group having an alkyl with 1 to 2 carbon atoms which may be substituted by a fluorine atom and/or a chlorine atom, an alkylthiocarbonyl group having an alkyl with 1 to 2 carbon atoms, a phenoycarbonyl group which may be substituted by a methyl group and/or a chlorine atom, a phenylthiocarbonyl group which may be substituted by a chlorine atom, a benzyloxycarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group, a benzoylaminocarbonyl group, a phenylsulfonylaminocarbonyl group which may be substituted by a methyl group and/or a chlorine atom, a phenylthio group, a methylsulfonyl which may be substituted by a chlorine atom, a phenylsulfonyl group which may be substituted by a methyl group, a methylcarbonylmethyl group, a phenacyl group which may be substituted by a chlorine atom, O,O-diethylthionophosphone group, O-ethyl-S-n-propylthiolophosphono group, --CH₂ --W or --CO--W, W represents a 5 to 6 membered heterocyclic group, containing one or two hetero atoms selected from the class consisting of an oxygen atom, a sulfur atom and a nitrogen atom, which may be substituted by a fluorine atom, a chlorine atom, a bromine atom and a methyl group, Y represents a nitrogen atom or ##STR691## R⁹ represents a hydrogen atom, a chlorine atom, a bromine atom, a hydroxy group, a methoxy group, a benzyloxy group, an alkyl group which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a hydroxy group, a methoxy group, a cyano group, a dimethylamino group, an acetyl group and a methoxycarbonyl group, an allyl group, a phenyl group, an acetyl group which may be substituted by a chlorine atom, a vinylcarbonyl group, an allylcarbonyl group, a benzoyl group, an alkoxycarbonyl group having an alkyl with 1 to 2 carbon atoms which may be substituted by a fluorine atom, n-butylthiocarbonyl group, a phenoxycarbonyl group which may be substituted by a chlorine atom and/or a methyl group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, a benzoylaminocarbonyl group which may be substituted by a chlorine atom, a phenylsulfonylaminocarbonyl group which may be substituted by a methyl group, a methylsulfonylaminocarbonyl group, a propylthio group, a methylsulfonyl group which may be substituted by a fluorine atom and/or a chlorine atom, a phenylthio group which may be substituted by a chlorine atom, or a phenylsulfonyl group, in addition, R⁹ may form a bis-form of the formula (I), via a methylene group, R represents a hydrogen or a methyl group, and Z represents a 5 to 6 membered heterocyclic group, containing one to three hetero atoms selected from the class consisting of an oxygen atom, a sulfur atom and a nitrogen atom, at least one of which is a nitrogen atom, which may be substituted by at least one member selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, fluoroalkyl groups having 1 to 2 carbon atoms, a methoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, a nitro group, a cyano group, a trifluoromethoxy group, a trifluoromethylthio group, an allyl group, an acetamide group, a methoxycarbonyl group, an acetyl group, a formyl group and a carboxyl group, provided that where R¹, R², R³, R⁴, R⁵ and R⁶ represent hydrogen atoms simultaneously, and Y represents ##STR692## then Z does not stand for an optionally substituted pyridyl group.
 3. 1-(1-Methyl-4-pyrazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR693##
 4. 1-(3-Trifluoromethyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR694##
 5. 1-(3-Methyl-5-isoxazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR695##
 6. 1(2-Chloro-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR696##
 7. 1-(1,2,5-Thiadiazol-3-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR697##
 8. 1-(1,2,3-Thiadiazol-5-ylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR698##
 9. 1-(2-Methyl-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR699##
 10. 1-(5-Thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR700##
 11. 1-(2-Chloro-5-pyrimidinylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR701##
 12. 1-(2-(Chloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR702##
 13. 1-(2-Chloro-5-thiazolylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 of the formula ##STR703##
 14. An insecticidal composition comprising an insecticidally effective amount of a compound according to claim 1 in admixture with a diluent.
 15. A method of combating insects which comprises applying to said insects or to an insect habitat an insecticidally effective amount of a compound according to claim
 1. 16. A compound according to claim 1, in which n represents
 1. 17. A compound according to claim 1, in which X is ##STR704## 